1,3,4-Thiadiazole-2-carboxylic acid derivatives, process for making the same and fungicidal and nematocidal compositions containing same

ABSTRACT

1,3,4-thiadiazole-2-carboxylic acid derivatives of the formula ##STR1## wherein R is C 1  -C 6  -alkyl, C 2  -C 6  -alkenyl, C 2  -C 6  -alkinyl or C 3  -C 6  -cycloalkyl, 
     R 1  is C 1  -C 6  -alkoxycarbonyl, aminocarbonyl, C 1  -C 8  -alkylaminocarbonyl, C 3  -C 6  -cycloalkylaminocarbonyl, di-C 1  -C 8  -alkylaminocarbonyl, cyclohexylmethylaminocarbonyl, alkoxyalkylaminocarbonyl, morpholinocarbonyl, pyrrolidinocarbonyl, piperidinocarbonyl or cyano, 
     and n is 0.1 or 2. 
     The compounds where n is 1 or 2 have both a high fungicidal and nematocidal activity. The compounds in which n is 0 are the starting products or intermediate products in making the compound in which a sulfonyl or sulfinyl group is present (n=1 or 2) but have also nematocidal properties of their own. All compounds of the invention avoid the undesirable environmental properties and other shortcomings of the prior art products, particularly those of the broadly used mercury compounds.

This is a division of application Ser. No. 101,061, filed Dec. 6, 1979.

BACKGROUND OF THE INVENTION

The invention relates to 1,3,4-thiadiazole-2-carboxylic acidderivatives.

Compounds for use against phytopathogenic fungi are already known.Compounds in use of this kind are for instancemanganeseethylene-bisdithiocarbamate (U.S. Pat. No. 2,504,404),N-trichloromethylmercaptotetrahydro-phthalimide andN-trichloromethylmercapto-phthalimide (U.S. Pat. No. 2,553,770, U.S.Pat. No. 2,553,771, U.S. Pat. No. 2,553,776),tetrachloroisophthalodinitrile (U.S. Pat. No. 3,290,353, U.S. Pat. No.3,331,735) as well as mercury-organic compositions.

Agents for simultaneous use against nematodes and pathogenic soil fungiare likewise known, for instance sodium N-methyldithiocarbamate (BritishPat. No. 789,690).

The object of the present invention is to provide agents of superioractivity or other superior properties which have simultaneouslyfungicidal and nematocidal effects.

ESSENCE OF THE INVENTION

The compounds of the invention have the formula ##STR2## wherein

R is C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl, C₂ -C₆ -alkinyl or C₃ -C₆-cycloalkyl,

R₁ is C₁ -C₆ -alkoxycarbonyl, aminocarbonyl, C₁ -C₈ -alkylaminocarbonyl,C₃ -C₆ -cycloalkylaminocarbonyl, di-C₁ -C₈ -alkylaminocarbonyl,cyclohexylmethylaminocarbonyl, alkoxyalkylaminocarbonyl,morpholinocarbonyl, pyrrolidinocarbonyl, piperidinocarbonyl or cyano and

n is 0, 1 or 2.

The compounds of the invention wherein n is 1 or 2 have a surprisinglybroad spectrum of activity against phytopathogenic fungi, superior toprior art agents of the type above listed. They also have a goodcompatibility with agricultural plants and an adequate duration of theiractivity. They have furthermore the advantage that they are alsoeffective against nematodes in which case they can be used, contrary tothe prior art nematocidal compounds, without a waiting time betweentheir use and the planting period because of their high plantcompatibility. Thus, they permit a problem-free action against pests. Afurther advantage is that compared to the toxicologically objectionablemercury compounds they are environmentally acceptable.

Due to these properties the compounds of the invention can be used bothin agricultural operations and in horticulture for treatment of the soilor for application to the leaves, etc.

The compounds of the invention wherein n is 1 or 2 have a superioractivity against a large number of noxious fungi such as for instancePythium ultimum, Penicillium digitatum, Botrytis cinerea, Alternariasolani, Fusarium avenaceum, Tilletia caries, Helminthosporium gramineum,Ustilago avenae, Piricularia oryzae and others.

The nematocidal activity is also effective against many genera ofnematodes, for instance Meloidogyne sp., Rotylenchus, Pratylenchus,Tylenchorhynchus and others.

In the above formula I, R should preferably be methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, pentyl, isopentyl,neopentyl, hexyl, isohexyl, 2-propenyl, 2-propinyl, cyclopropyl andcyclohexyl.

R₁ preferably should be methoxycarbonyl, ethoxycarbonyl, aminocarbonyl,methylaminocarbonyl, butylaminocarbonyl, dimethylaminocarbonyl,cyclopropylaminocarbonyl, propylaminocarbonyl, isopropylaminocarbonyl,(N-butyl-N-methyl)-aminocarbonyl, (2-methoxyethyl)-aminocarbonyl,(3-methoxypropyl)-aminocarbonyl and cyano.

The compounds of the invention can either be used individually orintermixed with each other or intermixed with other active agents. Ifdesired, other fungicidal, nematocidal or insecticidal compounds orother pesticides may be used depending on the specific purpose.

The compounds may be used in the form of compositions such as powders,dusting agents, granulates, solutions, emulsions or suspensions. Thereshould then be added liquid and/or solid carrier materials or diluentsand if desired surface active agents.

Suitable liquid carrier materials are water, mineral oils, or otherorganic solvents such as xylene, chlorobenzene, cyclohexanol, dioxane,acetonitrile, acetic ester, dimethylformamide, isophoron anddimethylsulfoxide.

As solid carrier materials there may be used lime, kaolin, chalk, talc,attaclay and other clays as well as natural or synthetic silicic acid.

If surface active agents are added they may for instance be salts oflignosulfonic acids, salts of alkylated benzoesulfonic acids, sulfonicacid amides and their salts, polyethoxyamines and alcohols.

If the agents are used for seed treatment there may be added dyestuffsin order to give the treated seed material a distinct coloration.

The fraction of the active agent or agents can be varied within a broadrange. The particular concentration of the agents depends mainly on theamount of agent actually employed. For instance the total compositionsmay contain about 1 to 95% by weight, preferably 20 to 50% by weight, ofactive agent or agents and about 99 to 5% by weight of liquid or solidcarrier materials. Part of the carrier materials may be replaced by upto 20% by weight of surface active agents.

The compositions may be applied in conventional form, for instance byspraying, dusting, fogging, gasifying, smoke formation, spreading,pouring or otherwise.

PROCESS OF MAKING THE PREFERRED COMPOUNDS

The compounds of the invention wherein n is 1 or 2 can be formed invarious ways.

(A) Compounds of the formula ##STR3## in which R and R₁ have the samemeaning as in the above formula I and n is 0, are treated with oxidizingagents, preferably organic hydroperoxides, per-acids or inorganicoxidizing agents, in equimolar amounts dissolved in an inert solvent.

(B) Compounds of the invention wherein R₁ is a carboxylic acid amideresidue can be made by reacting the compounds of the above formula IIwherein, however, R₁ is C₁ -C₆ -alkoxycarbonyl with a suitable aminefollowed by treatment with an oxidizing agent as under A.

(C) If the compounds of formula I are intended to be of the type whereinR₁ is cyano they can be made by treating compounds of the above formulaII wherein R₁ is aminocarbonyl with a dehydration agent followed bytreatment with an oxidizing agent as described above at A.

(D) If the compounds of the invention are intended to be of the typewherein R₁ is a carboxylamide residue they can be made by reactingcompounds of the formula

    R.sub.1 "--CO--NH--NH.sub.2,

wherein R₁ " constitutes a carboxylic amide residue as listed withcarbondisulfide in the presence of a base so as to form a compound ofthe formula

    R.sub.1 "--CO--NH--NH--CS--S.sup.(-) Me.sup.(+).

The latter product is then reacted with an alkylating agent to form acompound of the formula

    R.sub.1 "--CO--NH--NH--CS--S--R

whereupon it is treated with a dehydration agent and an oxidizing agentin order to obtain the desired compounds of the invention.

(E) If compounds are wanted of the type of formula I in which R₁ is acarboxylic acid residue, the proceeding could be as follows: a compoundof the formula

    H.sub.2 N--NH--CS--S.sup.(-) Me.sup.(+)

is reacted with an alkylating agent to form a compound of the formula

    H.sub.2 N--NH--CS--S--R.

The latter reaction product is then treated with a compound of theformula

    R.sub.1 --CO--CO--Cl

in which R₁ is C₁ -C₆ -alkoxycarbonyl so as to form a carboxylic acidderivative of the above formula II, the reaction being carried out underdehydrating conditions. The last obtained reaction product is thentreated with an oxidizing agent as stated above at A.

In all these compounds R and R₁ have the meaning as in Formula I exceptas stated and Me.sup.(+) is a cation of an organic or inorganic base.

II. PROCESS FOR MAKING THE COMPOUNDS USED AS STARTING PRODUCTS BUT ALSOAS FINAL PRODUCTS (n=0)

The compounds of the formula I wherein n is 0 and which have not beendisclosed heretofore can be made as follows:

Compounds of the formula

    R.sub.1 '--CO--NH--NH.sub.2

in which R₁ ' is C₁ -C₆ -alkoxycarbonyl are reacted with carbondisulfide in the presence of a base so as to form a compound of theformula

    R.sub.1 '--CO--NH--NH--CS--S.sup.(-) Me.sup.(+).

The latter reaction product is then reacted with a dehydration agent soas to form a compound of the formula ##STR4## The latter compounds aresubjected to the action of an alkylating agent, if desired in thepresence of a base. There are thus formed the desired compounds of theformula ##STR5## The latter may be further reacted with suitable aminesto form compounds of the formula ##STR6## In all of these formulas R andR₁ have the meaning as in formula I unless otherwise indicated,Me.sup.(+) is the cation of an inorganic or organic base and R₁ " is acarboxylic amide residue or a cyano group.

III. DETAILS OF THE PROCESS OF MAKING

In order to make the compounds of the invention in which in the generalformula I n=1 there may be used as oxidizing agents organichydroperoxides such as tert.-butylhydroperoxide, or per-acids, such asm-chloroperbenzoic acid, or N-halogeno acid amides likeN-bromosuccinimide. Inorganic oxidizing agents, such as hydrogenperoxide and sodium metaperiodate may also be used. Preferably twooxidation equivalents of the oxidizing agents or a small excess areemployed per mol of thio compound at temperatures of about 0° to 60° C.

In order to make the compounds of the formula I in which n is 2 it ispossible in addition to the just named oxidizing agents to use alsoagents such as chlorine, potassium permanganate, chromic acid and theirsalts or nitric acid and the temperature range of 0° to 120° C.Preferably, there are used four oxidation equivalents or a slight excessabove it per mol of thio compound. In other words, there are used abouttwice the amount of oxidizing agents as employed for the above-describedsulfoxidation as in the case where n is 1.

The reaction in general can be carried out at temperatures between -30°and 120° C. These temperatures should be used during the oxidationreactions.

For the synthesis of the compounds of the invention the reactants areused in about equimolar amounts. This is otherwise in case of thedehydration reaction in which a large excess of the water extractingagent is preferred.

As reaction media there may be used solvents which are inert towards thereactants. They may be used as such or in mixture with water. Theirselection depends on conventional considerations having in mind thespecific purpose of the reaction. As solvents or suspension agents theremay be used: carboxylic acids such as acetic acid, carboxylic amides,such as dimethylformamide; carboxylic acid nitriles, such asacetonitrile; alcohols, such as methanol; ethers, such as dioxane, andmany others.

If it is considered advisable there may be used as inorganic or organicbases, oxides and hydroxides of the alkali or alkali earth metals, forinstance sodium or potassium hydroxide or tertiary amines, such astriethylamine or N,N-dimethylaniline.

Suitable alkylating agents are for instance alkyl halides, preferablyiodides and bromides, as well as esters of sulfuric acid, such asdimethylsulfate or esters of aromatic sulfonic acids, such asmethyltosylate.

Suitable dehydration agents are particularly inorganic agents, such asmineral acids, for instance concentrated sulfuric acid or polyphosphoricacid, inorganic halides, for instance, phosphorus pentachloride,phosphorus trichloride, titanium tetrachloride and many others. Alsoorganic agents may be used such as carboxylic acid chlorides, forinstance acetylchloride, carboxylic acid anhydride, such astrifluoroacetic acid anhydride, carbodiimides, such asdicyclohexylcarbodiimide and many others. The isolation of the formedcompounds of the invention may be carried out by distilling off thesolvent at atmospheric or reduced pressure or by precipitation withwater or a slightly polar organic solvent such as diethylether or bycrystallization.

PREFERRED EMBODIMENTS OF THE INVENTION

Examples for compounds wherein n is 1 or 2:

The following examples will illustrate the making of compounds of theinvention as shown in Formula I wherein n is 1 or 2.

EXAMPLE 1 5-ethylsulfonyl-1,3,4-thiadiazole-2-carboxylic acid ethylamide

A solution of 20.0 g of 5-ethylthio-1,3,4-thiadiazole-2-carboxylic acidethylamide in 70 ml of acetic acid is heated to 80° C. When thistemperature is reached 31.3 g of a 30% concentration of aqueous hydrogenperoxide are added dropwise resulting in boiling of the solution. Whenno more heat development is observed the solution is subjected toanother hour of reflux boiling whereupon it is cooled to roomtemperature, stirred in ice water and subjected to removal by suction ofthe precipitated compound.

Yield: 17.8 g (78% of the theoretical value); M.p.: 116° C.

EXAMPLE 2 5-ethylsulfinyl-1,3,4-thiadiazole-2-carboxamide

38 g of 5-ethylthio-1,3,4-thiadiazole-2-carboxamide are dissolved at 40°C. in 400 ml of glacial acetic acid and are then slowly reacted with22.6 ml of a 30% hydrogen peroxide upon stirring. The solution is keptfor another 3 hours at the same temperature. At the end of this periodthe oxidation is sufficiently complete not to require any furtheraddition of heat. After standing overnight the reaction mixture isstirred into two liters of icewater resulting in the precipitation of asolid material which is removed by suction and recrystallized fromisopropanol.

Yield: 15.2 g (37% of the theoretical value); M.p.: 103° C.

EXAMPLE 3 5-methylsulfonyl-1,3,4-thiadiazole-2-carboxamide

9.3 g of 5-methylthio-1,3,4-thiadiazole-2-carboxamide were dissolved at80° C. in 50 ml acetic acid and were reacted with 18 ml of 30% hydrogenperoxide upon stirring so as to permit to keep the solution duringboiling under reflux. After the addition is complete the boiling wascontinued for 30 minutes. After cooling to room temperature the reactionproduct precipitated. It was removed by suction and dried.

Yield: 7.3 g (67% of the theoretical value); M.p.: 185° C.

EXAMPLE 4 5-isopropylsulfonyl-1,3,4-thiadiazole-2-carbonitrile

40 ml of 30% hydrogen peroxide were added dropwise under stirring at 70°C. to a solution of 46.0 g of5-isopropylthio-1,3,4-thiadiazole-2-carboxamide in 250 ml of glacialacetic acid. This caused the solution to boil. Then 40 ml of perhydrolwere furthermore added causing the reaction solution to remain boilingwithout addition of any heat. The mixture was then subjected to stirringfor another 30 minutes whereupon it was cooled which caused the reactionproduct to crystallize out at 30° C. By adding icewater theprecipitation was completed. The crystallate was removed by suction anddried in a vacuum.

Yield: 45.0 g (86% of the theoretical amount); M.p.: 162° C.

EXAMPLE 5 5-methylsulfonyl-1,3,4-thiadiazole-2-carbonitrile

A mixture of 20 ml titanium tetrachloride in 50 ml carbon tetrachloridewas added dropwise at 0° to 5° C. upon stirring to 350 mltetrahydrofuran. Subsequently,2-methylsulfonyl-1,3,4-thiadiazole-2-carboxamide was added in batches atroom temperature in an amount of 20.7 g. After continued stirring for 1hour a solution of 50 ml triethylamine in 50 ml tetrahydrofuran wasdropped into the mixture within a period of 60 minutes. The mixture wasthen reacted with 50 ml water, the total mixture was extracted withchloroform and the organic phase was dried over magnesium sulfate andthe solvent was distilled off in a vacuum. The residue was taken up inacetic acid ethylester, subjected to boiling with activated carbon,filtered and concentrated. The residue was crystallized fromchloroform/tetrahydrofuran (3:1).

Yield: 9.1 g (48% of the theoretical value); M.p.: 173°-175° C.

EXAMPLE 6 5-methylsulfonyl-1,3,4-thiadiazole-2-carboxylic acidethylester

21.4 g of powdered potassium permanganate was introduced into a solutionof 20.4 g of 5-methylthio-1,3,4-thiadiazole-2-carboxylic acid ethylesterin 100 ml acetic acid and 40 ml water in a manner that the temperatureof the solution rose to 70° C. To complete the reaction the mixture wasstirred for another 30 minutes. Thereafter, the manganese dioxide whichprecipitated at 10° was reduced with a solution of 19 g sodiummetabisulfite in 100 ml water while cooling with ice. Upon addition of500 ml water the desired compound precipitated. It was removed bysuction, dried and recrystallized from isopropylether.

Yield: 9.4 g (40% of the theoretical value); M.p.: 48° C.

EXAMPLE 7 5-methylsulfonyl-1,3,4-thiadiazole-2-carboxylicacid-cyclohexylmethylamide

20.3 g of 5-methylthio-1,3,4-thiadiazole-2-carboxylic acidcyclohexylmethylamide were dissolved in 130 ml acetic acid and 25 mlwater. 16 g pulverized potassium permanganate was then introduced uponstirring to cause the temperature to increase to 70° C. Thereafter,stirring was continued for 30 minutes. The mixture was cooled and thenmixed with 300 ml ice water. The formed manganese dioxide was reducedwith a solution of 14.3 g sodium metabisulfite in 100 ml water. Theprecipitated compound was removed by suction and recrystallized fromethanol.

Yield: 18.3 g (81% of the theoretical value); M.p.: 159° C.

In an analogous manner to the Examples 1 to 7 the following specificcompounds were made:

    ______________________________________                                                                 Physical                                             Compound                 constants                                            ______________________________________                                        5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxamide            M.p.: 143° C.                                 5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carbonitrile           M.p.: 87° C.                                  5-isopropylsulfonyl-1,3,4-thiadiazole-                                        2-carbonitrile           M.p.: 78° C.                                  5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid methylamide                                                                          M.p.: 135° C.                                 5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-dimethylamide                                                                        M.p.: 91° C.                                  5-isobutylsulfonyl-1,3,4-thiadiazole-2-                                       carboxamide              M.p.: 125° C.                                 5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-methylamide                                                                          M.p.: 169° C.                                 5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-dimethylamide                                                                        M.p.: 58° C.                                  5-propylsulfonyl-1,3,4-thiadiazole-                                           2-carboxamide            M.p.: 153° C.                                 5-propylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-methylamide                                                                          M.p.: 148° C.                                 5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-butylamide                                                                           M.p.: 77° C.                                  5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-ethylester                                                                           M.p.: 55° C.                                  5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-cyclopropylamide                                                                     M.p.: 135° C.                                 5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-methylester                                                                          M.p.: 95° C.                                  5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-propylamide                                                                          M.p.: 105° C.                                 5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-(N-butyl,N-methyl)-                                                                  n.sub.D.sup.20 : 1,5310                              amide                                                                         5-ethylsulfonyl-1,3,4-thiadiazole-2-                                          carboxylic acid-(2-methoxyethyl)-amide                                                                 M.p.: 77° C.                                  5-ethylsulfonyl-1,3,4-thiadiazole-2-                                          carboxylic acid-(3-methoxypropyl)-amide                                                                M.p.: 71° C.                                  5-ethylsulfonyl-1,3,4-thiadiazole-2-                                          carboxylic acid-isopropylamide                                                                         M.p.: 85° C.                                  5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-allylamide                                                                           M.p.: 61° C.                                  5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-octylamide                                                                           M.p.: 82° C.                                  5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-N,N-tetramethylene-                                         amide                    M.p.: 91° C.                                  5-ethylsulfonyl-1,3,4-thiadiazole-2-                                          carboxylic acid-(N,N-3-oxapentamethy-                                         leneamide                M.p.: 83° C.                                  5-ethylsulfonyl-1,3,4-thiadiazole-2-                                          carboxylic acid-cyclooctylamide                                                                        M.p.: 97° C.                                  5-propylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-ethylester                                                                           M.p.: 38° C.                                  5-propylsulfonyl-1,3,4-thiadiazole-                                           2-carbonitrile           M.p.: 83° C.                                  5-propylsulfinyl-1,3,4-thiadiazole-                                           2-carbonitrile           M.p.: 69° C.                                  5-ethylsulfinyl-1,3,4-thiadiazole-                                            2-carbonitrile           M.p.: 78° C.                                  5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-ethylamide                                                                           M.p.: 137° C.                                 5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-isopropylamide                                                                       M.p.: 108° C.                                 5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-propylamide                                                                          M.p.: 115° C.                                 5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-butylamide                                                                           M.p.: 95° C.                                  5-methylsulfinyl-1,3,4-thiadiazole-                                           2-carboxylic acid-propylamide                                                                          M.p.: 95° C.                                  5-methylsulfinyl-1,3,4-thiadiazole-                                           2-carboxylic acid-butylamide                                                                           M.p.: 88° C.                                  5-propylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-ethylamide                                                                           M.p.: 105° C.                                 5-propylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-propylamide                                                                          M.p.: 103° C.                                 5-propylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-allylamide                                                                           M.p.: 70° C.                                  5-sec.-butylsulfonyl-1,3,4-thiadia-                                                                    n.sub.D.sup.20 : 1,5168                              zole-2-carboxylic acid-ethylester                                             5-sec.-butylsulfonyl-1,3,4-thiadia-                                           zole-2-carboxamide       M.p.: 127° C.                                 5-methylsulfinyl-1,3,4-thiadia-                                               zole-2-carboxylic acid-allylamide                                                                      M.p.: 68° C.                                  5-sec.-butylsulfinyl-1,3,4-thiadia-                                           zole-2-carboxamide       M.p.: 87° C.                                  5-sec.-butylsulfonyl-1,3,4-thiadia-                                           zole-2-carbonitrile      M.p.: 57° C.                                  5-propylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-isopropylamide                                                                       M.p.: 79° C.                                  5-propylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-butylamide                                                                           M.p.: 88° C.                                  5-methylsulfonyl-1,3,4-thiadiazole-                                           2-2-carboxylic acid-allylamide                                                                         M.p.: 72° C.                                  5-propylsulfinyl-1,3,4-thiadiazole-                                           2-carboxylic acid-ethylamide                                                                           M.p.: 75° C.                                  5-propylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-propylamide                                                                            M.p.: 67° C.                                  5-propylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-allylamide                                                                             M.p.: 73° C.                                  5-propylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-isopropylamide                                                                         M.p.: 76° C.                                  5-methylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-(2-methoxyethyl)-amide                                                                 M.p.: 63° C.                                  5-methylsulfonyl-1,3,4-thiadiazole-2-                                         carboxylic acid-(2-methoxyethyl)-amide                                                                 M.p.: 80° C.                                  5-methylsulfonyl-1,3,4-thiadiazole-2-                                         carboxylic acid-(3-methoxypropyl)-amide                                                                M.p.: 97° C.                                  5-methylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-(3-methoxypropyl)-amide                                                                M.p.: 71° C.                                  5-methylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-ethylamide                                                                             M.p.: 118° C.                                 5-methylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-isopropylamide                                                                         M.p.: 77° C.                                  5-methylsulfonyl-1,3,4-thiadiazole-2-                                         carboxylic acid-cyclopropylamide                                                                       M.p.: 171° C.                                 5-methylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-cyclopropylamide                                                                       M.p.: 149° C.                                 5-methylsulfonyl-1,3,4-thiadiazole-2-                                         carboxylic acid-N,N-trimethylenamide                                                                   M.p.: 144° C.                                 5-methylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-N,N-trimethylenamide                                                                   M.p.: 135° C.                                 5-propylsulfonyl-1,3,4-thiadiazole-2-                                         carboxylic acid-sec.-butylamide                                                                        M.p.: 45° C.                                  5-propylsulfonyl-1,3,4-thiadiazole-2-                                         carboxylic acid-dimethylamide                                                                          M.p.: 75° C.                                  5-butylsulfonyl-1,3,4-thiadiazole-2-                                          carboxamide              M.p.: 135° C.                                 5-butylsulfinyl-1,3,4-thiadiazole-2-                                          carboxamide              M.p.: 105° C.                                 5-butylsulfonyl-1,3,4-thiadiazole-2-                                          carbonitrile             M.p.: 43° C.                                  5-isobutylsulfonyl-1,3,4-thiadiazole-2-                                       carbonitrile             M.p.: 72° C.                                  5-propylsulfonyl-1,3,4,-thiadiazole-2-                                        carboxylic acid-hexylamide                                                                             M.p.: 75° C.                                  5-isopropylsulfonyl-1,3,4-thiadiazole-                                        2-carboxylic acid-cyclohexylmethylamide                                                                M.p.: 134° C.                                 5-isopropylsulfinyl-1,3,4-thiadiazole-                                        2-carboxylic acid-cyclohexylmethylamide                                                                M.p.: 139° C.                                 5-propylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-butylamide                                                                             M.p.: 64° C.                                  5-propylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-sec.-butylamide                                                                        M.p.: 60° C.                                  5-propylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-hexylamide                                                                             M.p.: 68° C.                                  5-propylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-dimethylamide                                                                          M.p.: 64° C.                                  5-methylsulfinyl-1,3,4-thiadiazole-2-                                         carbonitrile             M.p.: 114° C.                                 5-methylsulfinyl-1,3,4-thiadiazole-                                           2-carboxamide            M.p.: 163° C.                                 5-isopropylsulfinyl-1,3,4-thiadiazole-                                        2-carboxamide            M.p.: 135° C.                                                          (decomposed)                                         5-isopropylsulfinyl-1,3,4-thiadiazole-                                        2-carbonitrile           n.sub.D.sup.20 : 1,5812                              5-pentylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-ethylester                                                                           n.sub.D.sup.20 : 1,5130                              5-pentylsulfonyl-1,3,4-thiadiazole-                                           2-carbonitrile           M.p.: 51° C.                                  5-hexylsulfonyl-1,3,4-thiadiazole-                                            2-carbonitrile           M.p.: 39° C.                                  5-pentylsulfonyl-1,3,4-thiadiazole-                                           2-carboxamide            M.p.: 151° C.                                 5-hexylsulfonyl-1,3,4-thiadiazole-                                            2-carboxamide            M.p.: 139° C.                                 5-propylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-N,N-trimethyleneamide                                                                M.p.: 127° C.                                 5-butylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-N,N-trimethyleneamide                                                                M.p.: 102° C.                                 5-butylsulfinyl-1,3,4-thiadiazole-                                            2-carbonitrile           M.p.: 68° C.                                  5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-N,N-trimethyleneamide                                                                M.p.: 107° C.                                 5-isopropylsulfonyl-1,3,4-thiadiazole-                                        2-carboxylic acid-methylamide                                                                          M.p.: 207° C.                                 5-isopropylsulfonyl-1,3,4-thiadiazole-                                        2-carboxylic acid-ethylamide                                                                           M.p.: 131° C.                                 5-isopropylsulfonyl-1,3,4-thiadiazole-                                        2-carboxylic acid-isopropylamide                                                                       M.p.: 111° C.                                 5-isopropylsulfonyl-1,3,4-thiadiazole-                                        2-carboxylic acid-propylamide                                                                          M.p.: 94° C.                                  5-isopropylsulfonyl-1,3,4-thiadiazole-                                        2-carboxylic acid-butylamide                                                                           M.p.: 72° C.                                  5-isopropylsulfonyl-1,3,4-thiadiazole-                                        2-carboxylic acid-isobutylamide                                                                        M.p.: 92° C.                                  5-isopropylsulfonyl-1,3,4-thiadiazole-                                        2-carboxylic acid-sec.-butylamide                                                                      M.p.: 92° C.                                  5-isopropylsulfinyl-1,3,4-thiadiazole-                                        2-carboxylic acid-methylamide                                                                          M.p.: 184                                                                     (decomposed)                                         5-isopropylsulfinyl-1,3,4-thiadiazole-                                        2-carboxylic acid-ethylamide                                                                           M.p.: 118° C.                                 5-(2-propenylsulfinyl)-1,3,4-thiadia-                                         zole-2-carboxylic acid-methylamide                                                                     M.p.: 125° C.                                 5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-N-ethyl-N-butylamide                                                                 n.sub.D.sup.20 : 1,5312                              5-isopropylsulfinyl-1,3,4-thiadiazole-                                        2-carboxylic acid-propylamide                                                                          M.p.: 84° C.                                  5-isopropylsulfonyl-1,3,4-thiadiazole-                                        2-carboxylic acid-isopropylamide                                                                       M.p.: 84° C.                                  5-isopropylsulfonyl-1,3,4-thiadiazole-                                        2-carboxylic acid-dimethylamide                                                                        M.p.: 82° C.                                  5-butylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-methylamide                                                                          M.p.: 146° C.                                 5-butylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-ethylamide                                                                           M.p.: 87° C.                                  5-butylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-propylamide                                                                          M.p.: 101° C.                                 5-butylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-(2-methoxyethyl)amide                                                                M.p.: 63° C.                                  5-butylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-isopropylamide                                                                       M.p.: 99° C.                                  5-butylsulfinyl-1,3,4-thiadiazole-                                            2-carboxylic acid-methylamide                                                                          M.p.: 112° C.                                 5-butylsulfinyl-1,3,4-thiadiazole-                                            2-carboxylic acid-ethylamide                                                                           M.p.: 72° C.                                  5-butylsulfinyl-1,3,4-thiadiazole-                                            2-carboxylic acid-propylamide                                                                          M.p.: 84° C.                                  5-butylsulfinyl-1,3,4-thiadiazole-                                            2-carboxylic acid-(2-methoxyethyl)-amide                                                               M.p.: 54° C.                                  5-butylsulfinyl-1,3,4-thiadiazole-                                            2-carboxylic acid-isopropylamide                                                                       M.p.: 57° C.                                  5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-N-butyl-N-methylamide                                                                n.sub.D.sup.20 : 1,5330                              5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-N-isobutyl-N-methyl-                                                                 n.sub.D.sup.20 : 1,5291                              5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-N,N-diethylamide                                                                     M.p.: 98° C.                                  5-sec.-butylsulfonyl-1,3,4-thiadiazole-                                       2-carboxylic acid-methylamide                                                                          M.p.: 150° C.                                 5-sec.-butylsulfonyl-1,3,4-thiadiazole-                                       2-carboxylic acid-ethylamide                                                                           M.p.: 79° C.                                  5-cyclohexylsulfonyl-1,3,4-thiadiazole-                                       2-carboxamide            M.p.: 176° C.                                 5-cyclohexylsulfonyl-1,3,4-thiadiazole-                                       2-carbonitrile           M.p.: 140° C.                                 5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-N,N-dipropylamide                                                                    M.p.: 55° C.                                  5-sec.-butylsulfonyl-1,3,4-thiadiazole-                                       2-carboxylic acid-cyclopropylamide                                                                     M.p.: 95° C.                                  5-pentylsulfinyl-1,3,4-thiadiazole-                                           2-carbonitile            M.p.: 65° C.                                  5-hexylsulfinyl-1,3,4-thiadiazole-                                            2-carbonitrile           M.p.: 57° C.                                  5-pentylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-methylamide                                                                          M.p.: 126° C.                                 5-hexylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-methylamide                                                                          M.p.: 108° C.                                 5-cyclohexylsulfinyl-1,3,4-thiadiazole-                                       2-carbonitrile           M.p.: 87° C.                                  5-sec.-butylsulfonyl-1,3,4-thiadiazole-                                       2-carboxylic acid-(2-methoxyethyl)-amide                                                               n.sub.D.sup.20 : 1,5357                              5-sec.-butylsulfinyl-1,3,4-thiadiazole-                                       2-carboxylic acid-methylamide                                                                          M.p.: 115° C.                                 5-sec.-butylsulfinyl-1,3,4-thiadiazole-                                       2-carboxylic acid-ethylamide                                                                           n.sub.D.sup.20 : 1,5580                              5-pentylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-ethylamide                                                                           M.p.: 90° C.                                  5-hexylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-ethylamide                                                                           M.p.: 67° C.                                  5-pentylsulfinyl-1,3,4-thiadiazole-                                           2-carboxylic acid-ethylamide                                                                           M.p.: 75° C.                                  5-hexylsulfinyl-1,3,4-thiadiazole-                                            2-carboxylic acid-ethylamide                                                                           M.p.: 75° C.                                  5-methylsulfinyl-1,3,4-thiadiazole-                                           2-carboxylic acid-N,N-diethylamide                                                                     n.sub.D.sup.20 : 1,5650                              5-sec.-butylsulfonyl-1,3,4-thiadiazole-                                       2-carboxylic acid-isopropylamide                                                                       M.p.: 77° C.                                  5-sec.-butylsulfinyl-1,3,4-thiadiazole-                                       2-carboxylic acid-cyclopropylamide                                                                     n.sub.D.sup.20 : 1,5671                              5-pentylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-propylamide                                                                          M.p.: 86° C.                                  5-pentylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-isopropylamide                                                                       M.p.: 95° C.                                  5-pentylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-cyclopropylamide                                                                     M.p.: 106° C.                                 5-pentylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-butylamide                                                                           M.p.: 92° C.                                  5-pentylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-sec.-butylamide                                                                      M.p.: 89° C.                                  5-pentylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-isobutylamide                                                                        M.p.: 106° C.                                 5-pentylsulfinyl-1,3,4-thiadiazole-                                           2-carboxylic acid-propylamide                                                                          M.p.: 79° C.                                  5-pentylsulfinyl-1,3,4-thiadiazole-                                           2-carboxylic acid-isopropylamide                                                                       M.p.: 61° C.                                  5-pentylsulfinyl-1,3,4-thiadiazole-                                           2-carboxylic acid-allylamide                                                                           M.p.: 74° C.                                  5-pentylsulfinyl-1,3,4-thiadiazole-                                           2-carboxylic acid-cyclopropylamide                                                                     M.p.: 90° C.                                  5-pentylsulfinyl-1,3,4-thiadiazole-                                           2-carboxylic acid-butylamide                                                                           M.p.: 85° C.                                  5-pentylsulfinyl-1,3,4-thiadiazole-                                           2-carboxylic acid-sec.-butylamide                                                                      M.p.: 59° C.                                  5-pentylsulfinyl-1,3,4-thiadiazole-                                           2-carboxylic acid-isobutylamide                                                                        M.p.: 80° C.                                  5-cyclopentylsulfonyl-1,3,4-thiadiazole-                                      2-carboxylic acid-methylamide                                                                          M.p.: 203° C.                                 5-cyclopentylsulfonyl-1,3,4-thiadiazole-                                      2-carboxylic acid-ethylamide                                                                           M.p.: 115° C.                                 5-sec.-butylsulfinyl-1,3,4-thiadiazole-                                       2-carboxylic acid-(2-methoxyethyl)-amide                                                               n.sub.D.sup.20 : 1,5519                              5-sec.-butylsulfonyl-1,3,4-thiadiazole-                                       2-carboxylic acid-(3-methoxypropyl)-amide                                                              n.sub.D.sup.20 : 1,5324                              5-cyclopentylsulfonyl-1,3,4-thiadiazole-                                      2-carboxylic acid-propylamide                                                                          M.p.: 95° C.                                  5-cyclopentylsulfonyl-1,3,4-thiadiazole-                                      2-carboxylic acid-isopropylamide                                                                       M.p.: 77° C.                                  5-cyclopentylsulfonyl-1,3,4-thiadiazole-                                      2-carboxylic acid-cyclopropylamide                                                                     M.p.: 90° C.                                  5-cyclopentylsulfonyl-1,3,4-thiadiazole-                                      2-carboxylic acid-butylamide                                                                           M.p.: 76° C.                                  5-cyclopentylsulfonyl-1,3,4-thiadiazole-                                      2-carboxylic acid-dimethylamide                                                                        M.p.: 56° C.                                  5-pentylsulfonyl-1,3,4-thiadiazole-2-                                         carboxylic acid-dimethylamide                                                                          M.p.: 61° C.                                  5-pentylsulfonyl-1,3,4-thiadiazole-2-                                         carboxylic acid-(3-methoxypropyl)-amide                                                                M.p.: 56° C.                                  5-hexylsulfonyl-1,3,4-thiadiazole-2-                                          carboxylic acid-propylamide                                                                            M.p.: 80° C.                                  5-hexylsulfonyl-1,3,4-thiadiazole-2-                                          carboxylic acid-isopropylamide                                                                         M.p.: 91° C.                                  5-hexylsulfonyl-1,3,4-thiadiazole-2-                                          carboxylic acid-(2-methoxyethyl)-amide                                                                 M.p.: 46° C.                                  5-hexylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-(3-methoxypropyl)-                                          amide                    M.p.: 57° C.                                  5-cyclopentylsulfinyl-1,3,4-thiadiazole-                                      2-carboxylic acid-methylamide                                                                          M.p.: 168° C.                                                          (decomposed)                                         5-cyclopentylsulfinyl-1,3,4-thiadiazole-                                      2-carboxylic acid-ethylamide                                                                           M.p.: 93° C.                                  5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-N,N-diisopropyl-                                            amide                    n.sub.D.sup.20 : 1,5240                              5-sec.-butylsulfinyl-1,3,4-thiadiazole-                                       2-carboxylic acid-(3-methoxypropyl)-                                          amide                    n.sub.D.sup.20 : 1,5489                              5-hexylsulfinyl-1,3,4-thiadiazole-                                            2-carboxylic acid-propylamide                                                                          M.p.: 71° C.                                  5-hexylsulfinyl-1,3,4-thiadiazole-                                            2-carboxylic acid-isopropylamide                                                                       M.p.: 61°  C.                                 5-hexylsulfinyl-1,3,4-thiadiazole-                                            2-carboxylic acid-(2-propenyl)-amide                                                                   M.p.: 69° C.                                  5-hexylsulfinyl-1,3,4-thiadiazole-                                            2-carboxylic acid-cyclopropylamide                                                                     M.p.: 90° C.                                  5-hexylsulfinyl-1,3,4-thiadiazole-                                            2-carboxylic acid-(2-methoxyethyl)-                                           amide                    M.p.: 57° C.                                  5-hexylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-cyclopropylamide                                                                     M.p.: 83° C.                                  5-hexylsulfinyl-1,3,4-thiadiazole-                                            2-carboxylic acid-(3-methoxypropyl)-                                          amide                    M.p.: 53° C.                                  ______________________________________                                    

The compounds of the invention are colorless and non-smelling oils orcrystalline bodies which have a good solubility in polar organicsolvents such as carboxylic acid amides, for instance dimethylformamide;carboxylic acid nitriles, for instance acetonitrile, and alcohols suchas methanol. They are less soluble in hydrocarbons, for instance hexane,and halogenated hydrocarbons, for instance dichloromethane. They areinsoluble in water.

Examples illustrating the starting products and compounds of theinvention wherein n=0

The following examples illustrate the making of the compounds of theinvention coming under formula I wherein n=0. These compounds arestarting products or intermediate products for making the compounds ofthe invention in which n is 1 or 2. However, in view of their partialnematocidal properties they may also be used directly as nematocides inagriculture and horticulture.

EXAMPLE 8 (a) 3-(ethoxyoxalyl)-dithiocarbazinic acid, potassium salt

91.5 g of carbon disulfide were added upon stirring to a suspension of198 g of oxalic acid ethylesterhydrazide in 1 l ethanol while stirring.At a temperature between 10° and 15° C. there was then added dropwise asolution of 98.7 g of 85% concentration potassium hydroxide in 900 mlethanol. Stirring was continued for 1 hour and the formed salt wasextracted with 3 l diethylether. The potassium salt was removed bysuction, washed with ether and dried in a vacuum.

Yield: 357 g (97% of the theoretical amount); M.p.: 160° C.

(b) 5-thioxo-1,3,4-thiadiazoline-2-carboxylic acid ethylester

440 g of the product obtained in (a), that is3-(ethoxyoxalyl)-dithiocarbazinic acid, potassium salt were introducedinto 1.2 l concentrated sulfuric acid at a temperature of 20°-30° C. Themixture was stirred until the compounds was completely dissolved. Afterstanding overnight the solution was stirred in 5 l icewater. Thepercipitated compound was removed by suction, washed with water, anddried in a vacuum at 40° C.

Yield: 163.5 g (48% of the theoretical value); M.p.: 91° C.

(c) 5-ethylthio-1,3,4-thiadiazole-2-carboxylic acid ethylester

99.9 g of ethyliodide were added to a suspension of 121.3 g of thecompound obtained in (b), i.e. 5-thioxo-1,3,4-thiadiazoline-2-carboxylicacid ethylester in 350 ml ethanol. Thereafter, 64.7 g of triethylaminewere added dropwise at a temperature between 20° and 25° C. whilecooling and stirring the mixture. Stirring was then continued foranother 2 hours. The mixture was thereafter poured into 1.5 l icewater.The precipitating oil was extracted with 300 ml chloroform. Thechloroform phase was separated, twice washed with water and dried onmagnesium sulfate. The solvent was distilled off at a reduced pressure.

Yield: 99.3 g (71% of the theoretical value); n_(D) ²⁰ : 1,5782.

EXAMPLE 9 5-ethylthio-1,3,4-thiadiazole-2-carboxylic acid ethylamide

54 g of an aqueous 50% ethylamine solution were added to 43.7 g of thecompound obtained in Example 8(c), that isethylthio-1,3,4-thiadiazole-2-carboxylic acid ethylester. This causedthe temperature to rise to 46° C. The solution was subsequently heatedto boiling point for another 15 minutes. It was then cooled to 4° C. andreacted with 50 ml icewater. The precipitated compound was removed bysuction.

Yield: 30.0 g (69% of the theoretical value); M.p.: 85° C.

EXAMPLE 10 5-methylthio-1,3,4-thiadiazole-2-carboxylic acid ethylester

61 g of dithiocarbazinic acid methylester were dissolved in 400 mldioxane. By adding dropwise upon stirring 75 g of oxalic acidethylesterchloride, the temperature was caused to rise to 75° C. At thistemperature the solution was subjected to further stirring for 30minutes. The dioxane was distilled off in a vacuum and the oily residuewas introduced in 350 ml of concentrated sulfuric acid. To complete thecyclization the reaction solution was kept for another hour at 40° C.and after cooling to room temperature was stirred into 2 l icewater. Theprecipitated crystals were removed by suction and recrystallized fromcyclohexane.

Yield: 68.5 g (67% of the theoretical value); M.p.: 46° C.

EXAMPLE 11 5-methylthio-1,3,4-thiadiazole-2-carboxamide

11.8 g of 5-methylthio-1,3,4-thiadiazole-2-carboxylic acid ethylesterwhich is the compound obtained in Example 10, were mixed with 50 mlethanol and 50 ml of a 25% aqueous ammonia solution whereupon themixture was heated for 15 minutes on a steam bath. After cooling part ofthe reaction product precipitated. The precipitation was completed byadding ice water. The precipitate was then removed by suction and driedin a vacuum.

Yield: 8.9 g (88% of the theoretical amount); M.p.: 185° C.

EXAMPLE 12 5-methylthio-1,3,4-thiadiazole-2-carbonitrile

350 ml tetrahydrofuran were added dropwise upon stirring and cooling ata temperature between 0° and 5° C. to a solution of 20 ml titaniumtetrachloride in 50 ml carbon tetrachloride. There were then added atfirst in batches 15.3 g of 5-methylthio-1,3,4-thiadiazole-2-carboxamideas obtained in Example 11, and thereafter within a period of 1 hour 50ml triethylamine which had been taken up in 50 ml tetrahydrofuran. Afteraddition of 50 ml water the reaction mixture was extracted withchloroform. The extract was dried on magnesium sulfate and the solventwas removed in a vacuum. The residue was taken up in acetic acidethylester and filtrated off from the insoluble residue. The ester phasewas then treated with activated carbon and finally concentrated todryness in a vacuum.

Yield: 11.1 g (81% of the theoretical amount); M.p.: 118°-120° C.

EXAMPLE 13 5-methylthio-1,3,4-thiadiazole-2-carboxylic acid cyclohexylmethylamide

30.6 g of 5-methylthio-1,3,4-thiadiazole-2-carboxylic acid ethylester asobtained in Example 10, were heated to boiling point for 2 hours with16.95 g of cyclohexylmethylamine in 150 ml ethanol. The solution wasconcentrated to 50 ml and the reaction product was precipitated bystirring in ice water.

Yield: 35.3 g (87% of the theoretical value); M.p.: 103° C.

In a manner analogous to the processes of Examples 8 to 13 the followingfurther starting products or intermediate products were obtained.

    ______________________________________                                                                 Physical                                             Compound                 Constants                                            ______________________________________                                        5-methylthio-1,3,4-thiadiazole-                                               2-carboxylic acid methylester                                                                          M.p.: 80° C.                                  5-methylthio-1,3,4-thiadiazole-                                               2-carboxylic acid methylamide                                                                          M.p.: 128° C.                                 5-methylthio-1,3,4-thiadiazole-                                               2-carboxylic acid dimethylamide                                                                        M.p.: 128° C.                                 5-ethylthio-1,3,4-thiadiazole-                                                2-carboxamide            M.p.: 162° C.                                 5-ethylthio-1,3,4-thiadiazole-                                                2-carboxylic acid methylamide                                                                          M.p.: 116° C.                                 5-ethylthio-1,3,4-thiadiazole-                                                2-carboxylic acid dimethylamide                                                                        M.p.: 53° C.                                  5-ethylthio-1,3,4-thiadiazole-                                                2-carboxylic acid cyclopropylamide                                                                     M.p.: 91° C.                                  5-ethylthio-1,3,4-thiadiazole-                                                2-carboxylic acid butylamide                                                                           M.p.: 54° C.                                  5-propylthio-1,3,4-thiadiazole-                                               2-carboxamide            M.p.: 137° C.                                 5-propylthio-1,3,4-thiadiazole-                                               2-carboxylic acid methylamide                                                                          M.p.: 72° C.                                  5-isopropylthio-1,3,4-thiadiazole-                                            2-carboxamide            M.p.: 154° C.                                 5-isobutylthio-1,3,4-thiadiazole-                                             2-carboxamide            M.p.: 162° C.                                 5-ethylthio-1,3,4-thiadiazole-2-                                              carbonitrile             M.p.: 40° C.                                  5-propylthio-1,3,4-thiadiazole-2-                                             carboxamide              M.p.: 142° C.                                 5-sec.-butylthio-1,3,4-thiadiazole-2-                                         carboxamide              M.p.: 119° C.                                 5-methylthio-1,3,4-thiadiazole-2-                                             carboxylic acid-propylamide                                                                            M.p.: 83° C.                                  5-methylthio-1,3,4-thiadiazole-2-                                             carboxylic acid-butylamide                                                                             M.p.: 90° C.                                  5-methylthio-1,3,4-thiadiazole-2-                                             carboxylic acid-allylamide                                                                             M.p.: 88° C.                                  5-methylthio-1,3,4-thiadiazole-2-                                             carboxylic acid-ethylamide                                                                             M.p.: 83° C.                                  5-methylthio-1,3,4-thiadiazole-2-                                             carboxylic acid-isopropylamide                                                                         M.p.: 101° C.                                 5-methylthio-1,3,4-thiadiazole-2-                                             carboxylic acid-(2-methoxyethyl)-amide                                                                 M.p.: 83° C.                                  5-methylthio-1,3,4-thiadiazole-2-                                             carboxylic acid-(3-methoxypropyl)-amide                                                                M.p.: 57° C.                                  5-methylthio-1,3,4-thiadiazole-2-                                             carboxylic acid-cyclopropylamide                                                                       M.p.: 130°   C.                               5-methylthio-1,3,4-thiadiazole-2-                                             carboxylic acid-N,N-trimethyleneamide                                                                  M.p.: 106° C.                                 5-butylthio-1,3,4-thiadiazole-2-                                              carboxamide              M.p.: 165° C.                                 5-hexylthio-1,3,4-thiadiazole-2-                                              carboxamide              M.p.: 150° C.                                 5-(2-methyl-2-propenylthio)-1,3,4-                                            thiadiazole-2-carboxylic acid-2-                                              propenylamide            n.sub.D.sup.20 : 1,5793                              5-(2-methyl-2-propenylthio)-1,3,4-                                            thiadiazole-2-carboxylic acid-iso-                                            propylamide              M.p.: 69° C.                                  5-(2-propenylthio)-1,3,4-thiadiazole-                                         2-(carboxylic acid amide M.p.: 144° C.                                 5-(2-propenylthio)-1,3,4-thiadiazole-2-                                       carboxylic acid-methylamide                                                                            M.p.: 87° C.                                  5-(2-propenylthio)-1,3,4-thiadiazole-                                         2-carboxylic acid-ethylamide                                                                           M.p.: 70° C.                                  5-(2-propenylthio)-1,3,4-thiadiazole-                                         2-carboxylic acid-propylamide                                                                          M.p.: 65° C.                                  5-(2-propenylthio)-1,3,4-thiadiazole-                                         2-carboxylic acid-isopropylamide                                                                       M.p.: 95° C.                                  5-(2-propenylthio)-1,3,4-thiadiazole-                                         2-carboxylic acid-(2-propenylamide)                                                                    M.p.: 54° C.                                  5-(2-propenylthio)-1,3,4-thiadiazole-                                         2-carboxylic acid-ethylester                                                                           n.sub.D.sup.20 : 1,5825                              5-butylthio-1,3,4-thiadiazole-2-                                              carboxylic acid-ethylester                                                                             n.sub.D.sup.20 : 1,5540                              5-butylthio-1,3,4-thiadiazole-2-                                              carboxylic acid-methylamide                                                                            M.p.: 83° C.                                  5-butylthio-1,3,4-thiadiazole-2-                                              carboxylic acid-propylamide                                                                            M.p.: 52° C.                                  5-butylthio-1,3,4-thiadiazole-2-                                              carboxylic acid ethylamide                                                                             M.p.: 67° C.                                  5-butylthio-1,3,4-thiadiazole-2-                                              carboxylic acid-isopropylamide                                                                         M.p.: 79° C.                                  5-isopropylthio-1,3,4-thiadiazole-2-                                          carboxylic acid-butylamide                                                                             M.p.: 53° C.                                  5-sec.-butylthio-1,3,4-thiadiazole-                                           2-carboxylic acid-ethylester                                                                           n.sub.D.sup.20 : 1,5527                              5-sec.-butylthio-1,3,4-thiadiazole-                                           2-carboxylic acid-methylamide                                                                          n.sub.D.sup.20 : 1,5762                              5-sec.-butylthio-1,3,4-thiadiazole-                                           2-carboxylic acid-ethylamide                                                                           n.sub.D.sup.20 : 1,5651                              5-cyclohexylthio-1,3,4-thiadiazole-                                           2-carboxamide            M.p.: 158° C.                                 5-(2-propinylthio)-1,3,4-thiadiazole-                                         2-carboxylic acid-amide  M.p.: 180° C.                                 5-pentylthio-1,3,4-thiadiazole-                                               2-carboxylic acid-methylamide                                                                          M.p.: 82° C.                                  5-hexylthio-1,3,4-thiadiazole-                                                2-carboxylic acid-methylamide                                                                          M.p.: 80° C.                                  5-sec.-butylthio-1,3,4-thiadiazole-                                           2-carboxylic acid-(2-methoxyethyl)-                                           amide                    n.sub.D.sup.20 : 1,5585                              5-sec.-butylthio-1,3,4-thiadiazole-                                           2-carboxylic acid-cyclopropylamide                                                                     M.p.: 50° C.                                  5-pentylthio-1,3,4-thiadiazole-                                               2-carboxylic acid-isobutylamide                                                                        M.p.: 80° C.                                  5-hexylthio-1,3,4-thiadiazole-                                                2-carboxylic acid-propylamide                                                                          M.p.: 61° C.                                  5-sec.-butylthio-1,3,4-thiadiazole-                                           2-carboxylic acid-(3-methoxypropyl)-                                          amide                    n.sub.D.sup.20 : 1,5566                              5-pentylthio-1,3,4-thiadiazole-                                               2-carboxylic acid-cyclopropylamide                                                                     M.p.: 87° C.                                  5-(2-propinylthio)-1,3,4-thiadiazole-                                         2-carboxylic acid-ethylester                                                                           M.p.: 57° C.                                  5-pentylthio-1,3,4-thiadiazole-                                               2-carboxylic acid-(2-propenyl)-amide                                                                   M.p.: 60° C.                                  5-hexylthio-1,3,4-thiadiazole-                                                2-carboxylic acid-(2-propenyl)-amide                                                                   M.p.: 90° C.                                  5-hexylthio-1,3,4-thiadiazole-                                                2-carboxylic acid-cyclopropylamide                                                                     M.p.: 54° C.                                  5-hexylthio-1,3,4-thiadiazole-2-                                              carboxylic acid-(2-methoxyethyl)-amide                                                                 M.p.: 52° C.                                  ______________________________________                                    

These compounds are soluble in carboxylic acids, carboxylic amides,carboxylic acid esters and halogenated hydrocarbons. They are lesssoluble in hydrocarbons and insoluble in water.

Examples illustrating uses and activities:

The following examples are furnished to illustrate the various uses andthe superior fungicidal activity of the compounds of the invention.

EXAMPLE 14 Threshold concentration test for use of the compounds againstPythium ultimum

A 20% concentration of certain pulverulent active agents as listed belowwere mixed in uniform manner into a soil which had been heavily infestedby Pythium ultimum. The thus treated soil was then placed into claydishes of a capacity of 0.5 l earth. Without any intermediate time lapse20 grain of garden peas (Pisum sativum L. convar. medullare Alef.) ofthe type "Wunder von Kelvedon" were then seaded into each of the claydishes. After a cultivation period of three weeks at 20° to 24° C. in ahothouse the number of sound peas was determined and a root evaluationwas carried out. The active agents amounts and results appear from thefollowing table.

The root evaluation was carried out on a scale from 1 to 4 as follows:

4=white roots without fungous necrosis;

3=white roots, minor fungous necrosis;

2=brown roots, already more pronounced fungous necrosis;

1=heavy fungous necrosis, roots rotted.

    ______________________________________                                                          Concentra-         root                                                       tion of   number   evalua-                                                    agent in  of sound tion                                     Active agent      mg/l soil peas     (1-4)                                    ______________________________________                                        5-methylsulfonyl-1,3,4-                                                                         20 mg     16       4                                        thiadiazole-2-carboxamide                                                                       40 mg     18       4                                                          80 mg     20       4                                        5-methylsulfonyl-1,3,4-                                                                         20 mg     17       3                                        thiadiazole-2-carbonitrile                                                                      40 mg     16       4                                                          80 mg     20       4                                        5-ethylsulfonyl-1,3,4-                                                                          20 mg     18       2                                        thiadiazole-2-carboxamide                                                                       40 mg     18       4                                                          80 mg     20       4                                        5-ethylsulfonyl-1,3,4-                                                                          20 mg     19       2                                        thiadiazole-2-carbonitrile                                                                      40 mg     20       4                                                          80 mg     20       4                                        5-ethylsulfinyl-1,3,4-                                                                          20 mg     15       2                                        thiadiazole-2-carboxamide                                                                       40 mg     20       4                                                          80 mg     20       4                                        5-isopropylsulfonyl-1,3,4-                                                                      20 mg     17       4                                        thiadiazole-2-carboxamide                                                                       40 mg     18       4                                                          80 mg     19       4                                        5-isopropylsulfonyl-1,3,4-                                                                      20 mg     18       2                                        thiadiazole-2-carbonitrile                                                                      40 mg     20       4                                                          80 mg     19       4                                        5-methylsulfonyl-1,3,4-                                                                         20 mg     20       4                                        thiadiazole-2-carboxylic                                                                        40 mg     18       4                                        acid-methylamide  80 mg     18       4                                        5-methylsulfonyl-1,3,4-                                                                         20 mg     18       4                                        thiadiazole-2-carboxylic                                                                        40 mg     20       4                                        acid-dimethylamide                                                                              80 mg     18       4                                        5-isobutylsulfonyl-1,3,4-                                                                       20 mg     15       1                                        thiadiazole-2-carboxamide                                                                       40 mg     18       4                                                          80 mg     18       4                                        5-ethylsulfonyl-1,3,4-                                                                          20 mg     17       4                                        thiadiazole-2-carboxylic                                                                        40 mg     15       4                                        acid-methylamide  80 mg     19       4                                        5-ethylsulfonyl-1,3,4-                                                                          20 mg     13       4                                        thiadiazole-2-carboxylic                                                                        40 mg     13       4                                        acid-dimethylamide                                                                              80 mg     15       4                                        5-propylsulfonyl-1,3,4-                                                                         20 mg     12       1                                        thiadiazole-2-carboxamide                                                                       40 mg     19       4                                                          80 mg     17       4                                        5-propylsulfonyl-1,3,4-                                                                         20 mg     19       4                                        thiadiazole-2-carboxylic                                                                        40 mg     16       4                                        acid-methylamide  80 mg     15       4                                        5-ethylsulfonyl-1,3,4-                                                                          20 mg     8        1                                        thiadiazole-2-carboxylic                                                                        40 mg     16       4                                        acid-butylamide   80 mg     20       4                                        5-ethylsulfonyl-1,3,4-                                                                          20 mg     15       4                                        thiadiazole-2-carboxylic                                                                        40 mg     16       4                                        acid-ethylamide   80 mg     16       4                                        5-methylsulfinyl-1,3,4-thia-                                                                    20 mg     19       4                                        diazole-2-carbonitrile                                                                          40 mg     20       4                                                          80 mg     20       4                                        5-ethylsulfinyl-1,3,4-thia-                                                                     20 mg     20       4                                        diazole-2-carbonitrile                                                                          40 mg     18       4                                                          80 mg     19       4                                        5-propylsulfinyl-1,3,4-thia-                                                                    20 mg     9        1                                        diazole-2-carbonitrile                                                                          40 mg     16       4                                                          80 mg     18       4                                        5-isopropylsulfinyl-1,3,4-                                                                      20 mg     17       3                                        thiadiazole-2-carbonitrile                                                                      40 mg     17       4                                                          80 mg     19       4                                        5-butylsulfinyl-1,3,4-thia-                                                                     20 mg     18       4                                        diazole-2-carbonitrile                                                                          40 mg     18       4                                                          80 mg     20       4                                        5-ethylsulfonyl-1,3,4-thia                                                                      20 mg     20       4                                        diazole-2-carboxylic acid-                                                                      40 mg     19       4                                        N,N-trimethylenamide                                                                            80 mg     20       4                                        5-propylsulfonyl-1,3,4-thia-                                                                    20 mg     6        1                                        diazole-2-carboxylic acid-                                                                      40 mg     19       4                                        N,N-trimethyleneamide                                                                           80 mg     18       4                                        5-propylsulfonyl-1,3,4-thia-                                                                    20 mg     10       1                                        diazole-2-carboxylic acid-                                                                      40 mg     19       3                                        (3-chloropropyl)-amide                                                                          80 mg     19       4                                        5-propylsulfinyl-1,3,4-thia-                                                                    20 mg     12       1                                        diazole-2-carboxylic acid-                                                                      40 mg     18       4                                        dimethylamide     80 mg     19       4                                        5-propylsulfonyl-1,3,4-thiadia-                                                                 20 mg     17       2                                        zole-2-carboxylic acid-                                                                         40 mg     20       4                                        dimethylamide     80 mg     19       4                                        5-methylsulfonyl-1,3,4-thia-                                                                    20 mg     19       4                                        diazole-2-carboxylic acid-                                                                      40 mg     18       4                                        allylamide        80 mg     18       4                                        5-methylsulfinyl-1,3,4-thia-                                                                    20 mg     20       4                                        diazole-2-carboxylic acid-                                                                      40 mg     19       4                                        allylamide        80 mg     18       4                                        5-ethylsulfonyl-1,3,4-thiadia-                                                                  20 mg     14       2                                        zole-2-carboxylic acid-tetra-                                                                   40 mg     20       4                                        methyleneamide    80 mg     20       4                                        5-propylsulfonyl-1,3,4-thia-                                                                    20 mg     9        1                                        diazole-2-carboxylic acid-                                                                      40 mg     20       4                                        isopropylamide    80 mg     18       4                                        5-propylsulfinyl-1,3,4-thia-                                                                    20 mg     15       2                                        diazole-2-carboxylic acid-                                                                      40 mg     19       4                                        allylamide        80 mg     19       4                                        5-methylsulfonyl-1,3,4-thia-                                                                    20 mg     9        1                                        diazole-2-carboxylic acid-                                                                      40 mg     20       4                                        (3-methoxypropyl)-amide                                                                         80 mg     19       4                                        5-methylsulfinyl-1,3,4-thia-                                                                    20 mg     18       2                                        diazole-2-carboxylic acid-                                                                      40 mg     18       4                                        ethylamide        80 mg     19       4                                        5-methylsulfinyl-1,3,4-thia-                                                                    20 mg     19       4                                        diazole-2-carboxylic acid-                                                                      40 mg     19       4                                        isopropylamide    80 mg     20       4                                        5-methylsulfonyl-1,3,4-thiadia-                                                                 20 mg     13       1                                        zole-2-carboxylic acid-                                                                         40 mg     20       4                                        cyclopropylamide  80 mg     20       4                                        5-methylsulfinyl-1,3,4-thia-                                                                    20 mg     15       1                                        diazole-2-carboxylic acid-                                                                      40 mg     20       4                                        cyclopropylamide  80 mg     20       4                                        5-methylsulfonyl-1,3,4-thia-                                                                    20 mg     19       4                                        diazole-2-carboxylic acid-                                                                      40 mg     20       4                                        N,N-trimethyleneamide                                                                           80 mg     20       4                                        5-methylsulfinyl-1,3,4-thia-                                                                    20 mg     12       2                                        diazole-2-carboxylic acid-                                                                      40 mg     16       4                                        N,N-trimethyleneamide                                                                           80 mg     19       4                                        5-butylsulfonyl-1,3,4-thia-                                                                     20 mg     11       1                                        diazole-2-carboxamide                                                                           40 mg     20       4                                                          80 mg     18       4                                        5-butylsulfinyl-1,3,4-thia-                                                                     20 mg     10       1                                        diazole-2-carboxamide                                                                           40 mg     15       4                                                          80 mg     19       4                                        5-methylsulfonyl-1,3,4-thia-                                                                    20 mg     15       4                                        diazole-2-carboxylic acid-                                                                      40 mg     15       4                                        ethylamide        80 mg     15       4                                        5-methylsulfonyl-1,3,4-thia-                                                                    20 mg     15       4                                        diazole-2-carboxylic acid-                                                                      40 mg     18       4                                        isopropylamide    80 mg     15       4                                        5-methylsulfonyl-1,3,4-thia-                                                                    20 mg     15       4                                        diazole-2-carboxylic acid-                                                                      40 mg     15       4                                        propylamide       80 mg     15       4                                        5-methylsulfonyl-1,3,4-thia-                                                                    20 mg     14       2                                        diazole-2-carboxylic acid-                                                                      40 mg     15       4                                        butylamide        80 mg     16       4                                        5-methylsulfinyl-1,3,4-thia-                                                                    20 mg     14       4                                        diazole-2-carboxylic acid-                                                                      40 mg     15       4                                        propylamide       80 mg     15       4                                        5-methylsulfinyl-1,3,4-thia-                                                                    20 mg     12       2                                        diazole-2-carboxylic acid-                                                                      40 mg     15       4                                        butylamide        80 mg     17       4                                        5-propylsulfonyl-1,3,4-thia-                                                                    20 mg     14       3                                        diazole-2-carboxylic acid-                                                                      40 mg     14       4                                        ethylamide        80 mg     14       4                                        5-propylsulfonyl-1,3,4-thia-                                                                    20 mg     10       1                                        diazole-2-carboxylic acid-                                                                      40 mg     16       4                                        propylamide       80 mg     16       4                                        5-propylsulfonyl-1,3,4-thia-                                                                    20 mg     13       3                                        diazole-2-carboxylic acid-                                                                      40 mg     15       4                                        allylamide        80 mg     15       4                                        5-ethylsulfonyl-1,3,4-thia-                                                                     20 mg     16       3                                        diazole-2-carboxylic acid-                                                                      40 mg     15       3                                        isopropylamide    80 mg     16       4                                        5-ethylsulfonyl-1,3,4-thia-                                                                     20 mg     11       1                                        diazole-2-carboxylic acid-                                                                      40 mg     17       4                                        allylamide        80 mg     16       4                                        5-ethylsulfonyl-1,3,4-thiadia-                                                                  20 mg     13       1                                        zole-2-carboxylic acid-                                                                         40 mg     16       4                                        (2-methoxyethyl)-amide                                                                          80 mg     16       4                                        5-ethylsulfonyl-1,3,4-thia-                                                                     20 mg     11       1                                        diazole-2-carboxylic acid-                                                                      40 mg     18       4                                        (3-methoxypropyl)-amide                                                                         80 mg     17       4                                        Comparison compounds                                                          Manganese ethylene-1,2-                                                                         20 mg     1        1                                        bis-dithiocarbamate                                                                             40 mg     4        1                                                          80 mg     11       1                                        N-trichloromethylmercapto-                                                                      20 mg     1        1                                        tetrahydro-phthalimide                                                                          40 mg     2        1                                                          80 mg     8        2                                        Control I. (3 times repeated)                                                 Infested soil; no treatment                                                                     --        1        1                                                          --        0        1                                                          --        0        1                                        Control II. (3 times repeated)                                                Humidified soil   --        18       4                                                          --        20       4                                                          --        17       4                                        ______________________________________                                    

EXAMPLE 15 Threshold concentration test in case of Fusarium avenaceum

A 20% pulverulent active agent of the type further identified in thetable below was mixed in uniform manner with a soil which had beenheavily infested with Fusarium a venaceum. The thus treated soil wasthen placed into clay dishes of a capacity of 0.5 l of earth. Each dishwas seeded without any intervening time with 20 grains of garden peas(Pisum sativum L. convar. medullare Alef.) of the type "Wunder vonKelvedon". After a cultivation time of 18 days at 20° to 24° C. in a hothouse the number of sound peas was determined and a root evaluation wascarried out. The active agents employed, the amounts and results appearfrom the following table.

The root evaluation was carried out on a scale from 1 to 4 as follows:

4=white roots without fungous necroses;

3=white roots with minor fungous necroses;

2=brown roots already more pronounced fungous necroses;

1=heavy fungous necroses with roots rotted.

    ______________________________________                                                          Concentra-         root                                                       tion of   number   evalua-                                                    agent in  of sound tion                                     Active agent      mg/l soil peas     (1-4)                                    ______________________________________                                        5-methylsulfinyl-1,3,4-thia-                                                                    25 mg     20       4                                        diazole-2-carbonitrile                                                                          50 mg     18       4                                                          100 mg    19       4                                        5-methylsulfonyl-1,3,4-thiadia-                                                                 25 mg     18       4                                        zole-carbonitrile 50 mg     17       4                                                          100 mg    19       4                                        5-ethylsulfinyl-1,3,4-thia-                                                                     25 mg     19       4                                        diazole-2-carbonitrile                                                                          50 mg     20       4                                                          100 mg    20       4                                        5-ethylsulfonyl-1,3,4-thia-                                                                     25 mg     18       4                                        diazole-2-carbonitrile                                                                          50 mg     20       4                                                          100 mg    20       4                                        5-propylsulfinyl-1,3,4-thia-                                                                    25 mg     19       4                                        diazole-2-carbonitrile                                                                          50 mg     20       4                                                          100 mg    19       4                                        5-propylsulfonyl-1,3,4-thia-                                                                    25 mg     10       4                                        diazole-2-carbonitrile                                                                          50 mg     20       4                                                          100 mg    20       4                                        5-isopropylsulfinyl-1,3,4-thia-                                                                 25 mg     18       4                                        diazole-2-carbonitrile                                                                          50 mg     19       4                                                          100 mg    18       4                                        5-isopropylsulfonyl-1,3,4-thia-                                                                 25 mg     20       4                                        diazole-2-carbonitrile                                                                          50 mg     20       4                                                          100 mg    19       4                                        5-butylsulfinyl-1,3,4-thia-                                                                     25 mg     19       4                                        diazole-2-carbonitrile                                                                          50 mg     19       4                                                          100 mg    19       4                                        5-butylsulfonyl-1,3,4-thia-                                                                     25 mg     18       4                                        diazole-2-carbonitrile                                                                          50 mg     20       4                                                          100 mg    20       4                                        5-sec.-butylsulfonyl-1,3,4-                                                                     25 mg     20       4                                        thiadiazole-2-carbonitrile                                                                      50 mg     19       4                                                          100 mg    20       4                                        5-isobutylsulfonyl-1,3,4-                                                                       25 mg     19       4                                        thiadiazole-2-carbonitrile                                                                      50 mg     20       4                                                          100 mg    19       4                                        5-pentylsulfonyl-1,3,4-                                                                         25 mg     20       4                                        thiadiazole-2-carbonitrile                                                                      50 mg     20       4                                                          100 mg    19       4                                        5-hexylsulfonyl-1,3,4-                                                                          25 mg     19       4                                        thiadiazole-2-carbonitrile                                                                      50 mg     19       4                                                          100 mg    19       4                                        5-pentylsulfonyl-1,3,4-thia-                                                                    25 mg     9        2                                        diazole-2-carboxamide                                                                           50 mg     16       3                                                          100 mg    18       4                                        5-hexylsulfonyl-1,3,4-                                                                          25 mg     7        1                                        thiadiazole-2-carboxamide                                                                       50 mg     12       2                                                          100 mg    15       3                                        5-propylsulfonyl-1,3,4-thia-                                                                    25 mg     11       2                                        diazole-2-carboxylic acid-                                                                      50 mg     17       3                                        N,N-trimethyleneamide                                                                           100 mg    17       3                                        5-n-butylsulfonyl-1,3,4-thia-                                                                   25 mg     5        1                                        diazole-2-carboxylic acid-                                                                      50 mg     13       2                                        N,N-trimethyleneamide                                                                           100 mg    18       3                                        5-propylsulfinyl-1,3,4-thia-                                                                    25 mg     9        3                                        diazole-2-carboxylic acid-                                                                      50 mg     13       4                                        isopropylamide    100 mg    16       4                                        5-methylsulfinyl-1,3,4-thia-                                                                    25 mg     7        2                                        diazole-2-carboxylic acid-                                                                      50 mg     11       3                                        (2-chlorobenzyleamide)                                                                          100 mg    18       4                                        5-butylsulfonyl-1,3,4-                                                                          25 mg     15       2                                        thiadiazole-2-carboxamide                                                                       50 mg     12       3                                                          100 mg    16       4                                        5-propylsulfinyl-1,3,4-thia-                                                                    25 mg     9        1                                        diazole-2-carboxylic acid-                                                                      50 mg     17       4                                        sec.-butylamide   100 mg    17       4                                        5-propylsulfonyl-1,3,4-                                                                         25 mg     14       2                                        thiadiazole-2-carboxylic                                                                        50 mg     16       3                                        acid-isopropylamide                                                                             100 mg    17       4                                        5-propylsulfonyl-1,3,4-                                                                         25 mg     9        1                                        thiadiazole-2-carboxylic                                                                        50 mg     16       3                                        acid-butylamide   100 mg    17       4                                        Comparison compound:                                                          3-trichloromethyl-5-ethoxy-                                                                     25 mg     0        1                                        1,2,4-thiadiazole 50 mg     0        1                                                          100 mg    0        1                                        Manganese-ethylene-1,2,-                                                                        25 mg     0        1                                        bis-dithiocarbamate                                                                             50 mg     0        1                                                          100 mg    12       1                                        Control I. (3 times repeated)                                                 Infested soil; no treatment                                                                     --        0        1                                                          --        0        1                                                          --        0        1                                        Control II. (3 times repeated)                                                Humidified soil   --        18       4                                                          --        20       4                                                          --        19       4                                        ______________________________________                                    

EXAMPLE 16 Inhibition of fungus in a nutrient solution

20 ml of a nutrient solution of graph juice and water (1:1) were filledinto a glass vial of a 100 ml capacity and were mixed with thepulverulent active agents which appear from the subsequent table.Thereafter, the solution was inoculated with conidia (spores) of thetest fungi.

After an incubation time of 6 days at 21 to 23° C. the fungusdevelopment on the surface of the nutrient solution was evaluated. Thetest fungi used were the following: Penicillium digitatum, Botrytiscinerea, Alternaria solani, Fusarium avenaceum.

The evaluation was carried out at a scale from 0 to 5 as follows:

0=no fungus growth;

1=isolated fungus colonies on the surface;

2=5 to 10% of the surface covered by the fungus turf;

3=10 to 30% of the surface covered by the fungus turf;

4=30 to 60% of the surface covered by the fungus turf;

5=60 to 100% of the surface covered by the fungus turf.

The active agent concentrations in the nutrient solution and the resultsappear from the following table.

    __________________________________________________________________________                 Concentration of                                                              agent in the                                                                           Penicillium                                                                         Botrytis                                                                           Alternaria                                                                          Fusarium                               Active agent nutrient solution                                                                      digitatum                                                                           cinerea                                                                            solani                                                                              avenaceum                              __________________________________________________________________________    5-methylsulfonyl-1,3,4-                                                                    0.002%   1     1    0     0                                      thiadiazole-2-carbonitrile                                                                 0.004%   0     0    0     0                                      5-ethylsulfonyl-1,3,4-                                                                     0.002%   0     1    0     0                                      thiadiazole-2-carbonitrile                                                                 0.004%   0     0    0     0                                      5-isopropylsulfonyl-1,3,4-                                                                 0.002%   0     1    0     0                                      thiadiazole-2-carbonitrile                                                                 0.004%   0     0    0     0                                      5-methylsulfonyl-1,3,4-                                                       thiadiazole-2-carboxylic                                                                   0.002%   1     1    1     0                                      acid-methylester                                                                           0.004%   0     0    0     0                                      5-ethylsulfonyl-1,3,4-                                                        thiadiazole-2-carboxylic                                                                   0.002%   1     2    0     1                                      acid-ethylester                                                                            0.004%   0     0    0     0                                      5-ethylsulfonyl-1,3,4-                                                        thiadiazole-2-carboxylic                                                                   0.002%   1     2    1     1                                      acid-butylamide                                                                            0.004%   0     0    0     0                                      5-isobutylsulfonyl-1,3,4-                                                                  0.002%   1     2    0     2                                      thiadiazole-2-carboxamide                                                                  0.004%   0     1    0     0                                      N-trichloromethylmer-                                                                      0.002%   4     4    4     4                                      capto-phthalimide                                                                          0.004%   4     3    4     4                                      N-trichloromethylmer-                                                         capto-tetrahydro-                                                                          0.002%   4     4    4     4                                      phthalimide  0.004%   4     4    4     4                                      Tetrachloroisophthalo-                                                                     0.002%   3     5    5     4                                      dinitrile    0.004%   2     4    5     3                                      Control: untreated                                                                         --       5     5    5     5                                      nutrient solution                                                             __________________________________________________________________________

EXAMPLE 17 Threshold concentration test with root gall nematodes(Meloidogyne sp.)

20% concentration pulverulent active agents as listed in the table belowwere mixed in a uniform manner with a soil which has been heavilyinfested by root gall nematodes. After waiting for 3 days the treatedsoil was placed in two clay dishes of a capacity of 0.5 liter. 10 grainof cucumber seeds of the type "Guntruud" were placed into each dish.

Thereafter, the contents of the dishes were permitted to develop at atemperature of 24° to 27° C. for a time of 28 days in a hothouse. Thecucumber roots were then washed out and were examined in a water bathregarding nematode infestation. The reduction of the infestation by theactive agents as compared with untreated control material was determinedin percentages.

The active agents amounts and reduction of infestation appear from thefollowing table.

The nematocidal activity was calculated by the formula ##EQU1##

In this formula

A=the infestation in the untreated control material and

B=the infestation after treatment.

    ______________________________________                                                     Percentage reduction of infestation                                           at the following agent concentra-                                             tions given in mg per liter soil                                 Active agent   200 mg    100 mg    50 mg                                      ______________________________________                                        5-methylsulfonyl-1,3,4-                                                                       96%      88%       71%                                        thiadiazole-2-carbonitrile                                                    5-methylthio-1,3,4-thia-                                                                     100%      99%       95%                                        diazole-2-carbonitrile                                                        ______________________________________                                    

EXAMPLE 18 Treatment of barley seeds infested with Helminthosporium gram

Barley seeds which all has a natural infestation by Helminthosporiumgram were seeded in plant pots filled with earth and left to germinationat a temperature below +16° C. Some of the seeds had not been treated,others had been treated with the active agents listed in the table.After emergence, the plants were subjected to illumination for 12 hoursper day. After about 5 weeks the infested plants were counted and thetotal number of plants for each test were also counted. The activeagents tested were used as pulverulent compositions.

The fungicidal activity was calculated as follows: ##EQU2##

    ______________________________________                                                          Amount of active                                                              agent in grams                                              Active agent      per 100 kg   % activity                                     ______________________________________                                        5-methylsulfonyl-1,3,4-                                                                         10           95                                             thiadiazole-2-carboxamide                                                                       20           100                                                              50           100                                            5-ethylsulfonyl-1,3,4-                                                                          10           97                                             thiadiazole-2-carboxamide                                                                       20           100                                                              50           100                                            5-ethylsulfinyl-1,3,4-                                                                          10           99                                             thiadiazole-2-carboxamide                                                                       20           100                                                              50           100                                            5-isopropylsulfonyl-1,3,4-                                                                      10           --                                             thiadiazole-2-carbonitrile                                                                      20           86                                                               50           97                                             5-methylsulfonyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           99                                             acid-methylamide  50           100                                            5-methylsulfonyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           87                                             acid-dimethylamide                                                                              50           98                                             5-isobutylsulfonyl-1,3,4-                                                                       10           --                                             thiadiazole-2-carboxamide                                                                       20           60                                                               50           87                                             5-ethylsulfonyl-1,3,4-                                                                          10           --                                             thiadiazole-2-carboxylic                                                                        20           91                                             acid-methylamide  50           97                                             5-ethylsulfonyl-1,3,4-                                                                          10           --                                             thiadiazole-2-carboxylic                                                                        20           94                                             acid-dimethylamide                                                                              50           100                                            5-ethylsulfonyl-1,3,4-                                                                          10           --                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-ethylamide   50           100                                            5-ethylsulfonyl-1,3,4-                                                                          10           --                                             thiadiazole-2-carboxylic                                                                        20           --                                             acid-propylamide  50           92                                             5-ethylsulfonyl-1,3,4-                                                                          10           --                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-(N-butyl-N-methyl)-amide                                                                   50           100                                            5-ethylsulfonyl-1,3,4-                                                                          10           100                                            thiadiazole-2-carboxylic                                                                        20           99                                             acid-(2-methoxyethyl)-amide                                                                     50           100                                            5-ethylsulfonyl-1,3,4-thia                                                                      10           99                                             diazole-2-carboxylic acid-                                                                      20           99                                             (3-methoxypropyl)-amide                                                                         50           100                                            5-ethylsulfonyl-1,3,4-                                                                          10           95                                             thiadiazole-2-carboxylic                                                                        20           98                                             acid-isopropyl-amide                                                                            50           100                                            5-ethylsulfonyl-1,3,4-                                                                          10           100                                            thiadiazole-2-carboxylic                                                                        20           100                                            acid-allylamide   50           100                                            5-ethylsulfonyl-1,3,4-                                                                          10           98                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-N,N-tetramethyleneamide                                                                    50           99                                             5-ethylsulfonyl-1,3,4-thia-                                                                     10           99                                             diazole-2-carboxylic acid-                                                                      20           100                                            (N,N-3-oxapentamethyleneamide)                                                                  50           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             cyclooctylamide   50           98                                             5-propylsulfinyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carbonitrile                                                                          20           87                                                               50           99                                             5-ethylsulfinyl-1,3,4-thia-                                                                     10           98                                             diazole-2-carbonitrile                                                                          20           100                                                              50           100                                            5-methylsulfonyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             ethylamide        50           93                                             5-methylsulfonyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             isopropylamide    50           90                                             5-methylsulfonyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             propylamide       50           93                                             5-methylsulfonyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             butylamide        50           90                                             5-methylsulfinyl-1,3,4-thia-                                                                    10           75                                             diazole-2-carboxylic acid-                                                                      20           98                                             propylamide       50           100                                            5-methylsulfinyl-1,3,4-thia-                                                                    10           67                                             diazole-2-carboxylic acid-                                                                      20           97                                             butylamide        50           100                                            5-sec.-butylsulfonyl-1,3,4-thia-                                                                10           --                                             diazole-2-carboxamide                                                                           20           --                                                               50           97                                             5-methylsulfinyl-1,3,4-thia-                                                                    10           94                                             diazole-2-carboxylic acid-                                                                      20           99                                             allylamide        50           100                                            5-methylsulfonyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             allylamide        50           100                                            5-propylsulfinyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             ethylamide        50           94                                             5-propylsulfinyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             propylamide       50           94                                             5-proptlsulfinyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             allylamide        50           96                                             5-propylsulfinyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             isopropylamide    50           100                                            5-methylsulfinyl-1,3,4-thia-                                                                    10           75                                             diazole-2-carboxylic acid-                                                                      20           97                                             (2-methoxyethyl)-amide                                                                          50           100                                            5-methylsulfonyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20 92                                                       (2-methoxyethyl)-amide                                                                          50           100                                            5-methylsulfinyl-1,3,4-                                                                         10           98                                             thiadiazole-2-carboxylic                                                                        20           99                                             acid-ethylamide   50           100                                            5-methylsulfinyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20 96                                                       isopropylamide    50           100                                            5-methylsulfinyl-1,3,4-thia-                                                                    10           72                                             diazole-2-carboxylic acid-                                                                      20           98                                             cyclopropylamide  50           99                                             5-methylsulfinyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20           95                                             N,N-trimethyleneamide                                                                           50           100                                            5-propylsulfonyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             dimethylamide     50           93                                             5-butylsulfinyl-1,3,4-thia-                                                                     10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             dimethylamide     50           100                                            5-propylsulfinyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             sec.-butylamide   50           94                                             5-propylsulfinyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             dimethylamide     50           100                                            5-methylsulfinyl-1,3,4-thia-                                                                    10           --                                             diadiazole-2-carbonitrile                                                                       20           --                                                               50           94                                             5-methylsulfinyl-1,3,4-thia-                                                                    10           --                                             diazole-2-carboxamide                                                                           20           --                                                               50           100                                            5-isopropylsulfinyl-1,3,4-thia-                                                                 10           --                                             diazole-2-carboxamide                                                                           20           --                                                               50           100                                            5-isopropylsulfinyl-1,3,4-thia-                                                                 10           --                                             diazole-2-carbonitrile                                                                          20           --                                                               50           93                                             Comparison compound                                                           Methoxyethyl-Hg-silicate                                                                        0.2          63                                                               0.5          91                                                               1.0          98                                             ______________________________________                                    

EXAMPLE 19 Treatment of oat seeds infested with Tilletia caries

Oat seeds were contaminated with 3 g of the spores of the stinking smuts(bunt) (Tilletia caries) per kg of seed material. Both untreated andtreated grains were then pressed with their hairy end into Petri dishesfilled with moist loam and were incubated at temperature below 12° C.for 3 days. The grains were subsequently removed and the Petri disheswere further incubated with the remaining smut spores at about 12° C.After 10 days the spores were examined regarding germination. The activeagents were employed in the form of pulverulent compositions.

The fungicidal activity was calculated on the basis of the followingformula: ##EQU3##

    ______________________________________                                                        Amount of active                                                              agent in grams                                                                per 100 kg % activity                                         ______________________________________                                        Active agent                                                                  5-ethylsulfonyl-1,3,4-thia-                                                                      5           87                                             diazole-2-carboxamide                                                                           10           93                                                               20           100                                            5-ethylsulfinyl-1,3,4-thia-                                                                      5           78                                             diazole-2-carboxamide                                                                           10           96                                                               20           100                                            5-methylsulfonyl-1,3,4-thia-                                                                     5           86                                             diazole-2-carboxylic acid-                                                                      10           99                                             cyclohexyl-methylamide                                                                          20           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           100                                            diazole-2-carboxylic acid-                                                                      20           100                                            methylamide       50           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           100                                            diazole-2-carboxylic acid-                                                                      20           100                                            dimethylamide     50           100                                            5-propylsulfonyl-1,3,4-thia-                                                                    10           100                                            diazole-2-carboxamide                                                                           20           100                                                              50           100                                            5-propylsulfonyl-1,3,4-thia-                                                                    10           99.5                                           diazole-2-carboxylic acid-                                                                      20           99.5                                           methylamide       50           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           100                                            diazole-2-carboxylic acid-                                                                      20           100                                            butylamide        50           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           85                                             diazole-2-carboxylic acid-                                                                      20           100                                            cyclopropylamide  50           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           99.3                                           diazole-2-carboxylic acid-                                                                      20           100                                            ethylamide        50           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           100                                            diazole-2-carboxylic acid-                                                                      20           100                                            propylamide       50           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           98                                             diazole-2-carboxylic acid-                                                                      20           100                                            (N-butyl-N-methyl)-amide                                                                        50           100                                            5-ethylsulfonyl)-1,3,4-thia-                                                                    10           100                                            diazole-2-carboxylic acid-                                                                      20           100                                            (2-methoxyethyl)-amide                                                                          50           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           100                                            diazole-2-carboxylic acid-                                                                      20           100                                            (3-methoxypropyl)-amide                                                                         50           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           100                                            diazole-2-carboxylic acid-                                                                      20           100                                            isopropyl-amide   50           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           100                                            diazole-2-carboxylic acid-                                                                      20           100                                            allylamide        50           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           91                                             diazole-2-carboxylic acid-                                                                      20           93                                             octylamide        50           98                                             5-ethylsulfonyl-1,3,4-thia-                                                                     10           100                                            diazole-2-carboxylic acid-                                                                      20           100                                            N,N-tetramethyleneamide                                                                         50           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           --                                             diazole-2-carboxylic acid-                                                                      20           --                                             (N,N-3-oxapentamethyleneamide                                                                   50           100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     10           100                                            diazole-2-carboxylic acid-                                                                      20           100                                            cyclooctylamide   50           100                                            5-propylsulfonyl-1,3,4-thia-                                                                    10           99                                             diazole-2-carbonitrile                                                                          20           100                                                              50           100                                            5-propylsulfinyl-1,3,4-thia-                                                                    10           99                                             diazole-2-carbonitrile                                                                          20           100                                                              50           100                                            5-ethylsulfinyl-1,3,4-thia-                                                                     10           99.8                                           diazole-2-carbonitrile                                                                          20           100                                                              50           100                                            5-methylsulfonyl-1,3,4-thia-                                                                    10           99.2                                           diazole-2-carboxylic acid-                                                                      20           99.2                                           ethylamide        50           98                                             5-methylsulfonyl-1,3,4-                                                                         10           100                                            thiadiazole-2-carboxylic acid-                                                                  20           100                                            isopropylamide    50           100                                            5-methylsulfonyl-1,3,4-thia-                                                                    10           99.5                                           diazole-2-carboxylic acid-                                                                      20           100                                            propylamide       50           100                                            5-methylsulfonyl-1,3,4-thia-                                                                    10           99.2                                           diazole-2-carboxylic acid-                                                                      20           100                                            butylamide        50           100                                            5-methylsulfinyl-1,3,4-                                                                         10           99                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-propylamide  50           100                                            5-methylsulfinyl-1,3,4-                                                                         10           99                                             thiadiazole-2-carboxylic                                                                        20           99.8                                           acid-butylamide   50           100                                            5-propylsulfonyl-1,3,4-                                                                         10           99.3                                           thiadiazole-2-carboxylic                                                                        20           99.8                                           acid-ethylamide   50           100                                            5-propylsulfonyl-1,3,4-                                                                         10           99.5                                           thiadiazole-2-carboxylic                                                                        20           99.7                                           acid-propylamide  50           100                                            5-propylsulfonyl-1,3,4-                                                                         10           99.3                                           thiadiazole-2-carboxylic                                                                        20           99.7                                           acid-allylamide   50           100                                            5-methylsulfinyl-1,3,4-                                                                         10           99.2                                           thiadiazole-2-carboxylic                                                                        20           100                                            acid-allylamide   50           100                                            5-sec.-butylsulfonyl-1,3,4-                                                                     10           75                                             thiadiazole-2-carbonitrile                                                                      20           91                                                               50           98                                             5-propylsulfonyl-1,3,4-                                                                         10           98                                             thiadiazole-2-carboxylic                                                                        20           99.8                                           acid-isopropylamide                                                                             50           100                                            5-propylsulfonyl-1,3,4-                                                                         10           99.2                                           thiadiazole-2-carboxylic                                                                        20           99.7                                           acid-butylamide   50           100                                            5-methylsulfonyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-allylamide   50           100                                            5-propylsulfinyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           99.3                                           acid-propylamide  50           100                                            5-propylsulfinyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-allylamide   50           100                                            5-propylsulfinyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-isopropylamide                                                                             50           100                                            5-methylsulfonyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           93                                             acid-(2-methoxyethyl)-amide                                                                     50           100                                            5-methylsulfinyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-ethylamide   50           100                                            5-methylsulfinyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-isopropylamide                                                                             50           100                                            5-methylsulfonyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           98                                             acid-cyclopropylamide                                                                           50           100                                            5-methylsulfinyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           98                                             acid-cyclopropylamide                                                                           50           100                                            5-methylsulfonyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           99                                             acid-N,N-trimethyleneamide                                                                      50           100                                            5-methylsulfinyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           96                                             acid-N,N-trimethyleneamide                                                                      50           100                                            5-propylsulfonyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-dimethylamide                                                                              50           100                                            5-butylsulfinyl-1,3,4-                                                                          10           --                                             thiadiazole-2-carboxamide                                                                       20           95                                                               50           100                                            5-butylsulfonyl-1,3,4-                                                                          10           --                                             thiadiazole-2-carbonitrile                                                                      20           95                                                               50           100                                            5-isobutylsulfonyl-1,3,4-                                                                       10           --                                             thiadiazole-2-carbonitrile                                                                      20           93                                                               50           100                                            5-propylsulfonyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-hexylamide   50           100                                            5-isopropylsulfonyl-1,3,4-                                                                      10           --                                             thiadiazole-2-carboxylic                                                                        20           92                                             acid-cyclohexylmethylamide                                                                      50           97                                             5-isopropylsulfinyl-1,3,4-                                                                      10           --                                             thiadiazole-2-carboxylic                                                                        20           99                                             acid-cyclohexylmethylamide                                                                      50           100                                            5-propylsulfinyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-butylamide   50           100                                            5-propylsulfinyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-sec.-butylamide                                                                            50           100                                            5-propylsulfinyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-hexylamide   50           100                                            5-propylsulfinyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           100                                            acid-dimethylamide                                                                              50           100                                            5-methylsulfinyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carbonitrile                                                                      20           100                                                              50           100                                            5-methylsulfinyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxamide                                                                       20           98                                                               50           100                                            5-isopropylsulfinyl-1,3,4-                                                                      10           --                                             thiadiazole-2-carboxamide                                                                       20           --                                                               50           100                                            5-isopropylsulfinyl-1,3,4-                                                                      10           --                                             thiadiazole-2-carbonitrile                                                                      20           87                                                               50           100                                            5-pentylsulfonyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carbonitrile                                                                      20           --                                                               50           90                                             5-hexylsulfonyl-1,3,4-                                                                          10           --                                             thiadiazole-2-carbonitrile                                                                      20           --                                                               50           90                                             5-pentylsulfonyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxamide                                                                       20           --                                                               50           80                                             5-hexylsulfonyl-1,3,4-                                                                          10           --                                             thiadiazole-2-carboxamide                                                                       20           --                                                               50           98                                             5-propylsulfonyl-1,3,4-                                                                         10           --                                             thiadiazole-2-carboxylic                                                                        20           --                                             acid-N,N-trimethyleneamide                                                                      50           100                                            5-n-butylsulfonyl-1,3,4-                                                                        10           --                                             thiadiazole-2-carboxylic                                                                        20           --                                             acid-N,N-trimethyleneamide                                                                      50           100                                            5-butylsulfinyl-1,3,4-                                                                          10           --                                             thiadiazole-2-carbonitrile                                                                      20           --                                                               50           100                                            Comparison compound                                                           methoxyethyl-Hg-silicate                                                                          1.3        90                                                                 2.6        100                                            ______________________________________                                    

EXAMPLE 20 Spray treatment of rice seedlings infested with Piriculariaoryzae

Young rice plants were sprayed so as to be dripping wet with the activeagent concentrations shown in the subsequent table. After drying of thespray deposits the treated plants as well as the untreated plants wereinoculated by spraying of a suspension of spores (about 200000/ml) ofthe Piricularia oryzae (the leaf smut cause), and were incubated inmoist condition at a temperature of 25° to 27° C. in a hothouse. After 5days it was determined which percentage of the leaf surface had beenaffected by the infestation.

The active compounds were employed in the form of pulverulentcompositions. From the infestation figures found the fungicidal activitywas determined on the basis of the following formula: ##EQU4##

    ______________________________________                                                         Concentration                                                                 of active agent                                                               (percentages)                                                                           % activity                                         ______________________________________                                        Active agent                                                                  5-methylsulfonyl-1,3,4-                                                                          0.02        --                                             thiadiazole-2-carboxamide                                                                        0.1         96                                             5-methylsulfonyl-1,3,4-                                                                          0.02        60                                             thiadiazole-2-carboxylic                                                                         0.1         80                                             acid-cyclohexyl-methylamide                                                   5-isopropylsulfonyl-1,3,4-                                                                       0.02        --                                             thiadiazole-2-carboxamide                                                                        0.1         40                                             5-isopropylsulfonyl-1,3,4-                                                                       0.02        --                                             thiadiazole-2-carbonitrile                                                                       0.1         94                                             5-methylsulfonyl-1,3,4-                                                       thiadiazole-2-carboxylic                                                                         0.02        65                                             acid-methylamide   0.1         91                                             5-methylsulfonyl-1,3,4-                                                       thiadiazole-2-carboxylic                                                                         0.02        91                                             acid-dimethylamide 0.1         98                                             5-isobutylsulfonyl-1,3,4-                                                                        0.02        65                                             thiadiazole-2-carboxamide                                                                        0.1         90                                             5-ethylsulfonyl-1,3,4-                                                        thiadiazole-2-carboxylic                                                                         0.1         90                                             acid-dimethylamide                                                            5-ethylsulfonyl-1,3,4-thia-                                                   diazole-2-carboxylic acid-                                                                       0.1         97                                             butylamide                                                                    5-ethylsulfonyl-1,3,4-thia-                                                   diazole-2-carboxylic acid-                                                                       0.1         95                                             ethylester                                                                    5-ethylsulfonyl-1,3,4-thia-                                                   diazole-2-carboxylic acid-                                                                       0.1         90                                             (2-methoxyethyl)-amide                                                        5-ethylsulfonyl-1,3,4-thia-                                                   diazole-2-carboxylic acid-                                                                       0.1         97                                             (3-methoxypropyl)-amide                                                       5-ethylsulfonyl-1,3,4-thia-                                                   diazole-2-carboxylic acid-                                                                       0.1         99                                             isopropylamide                                                                5-propylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                       0.1         93                                             ethylester                                                                    5-propylsulfonyl-1,3,4-thia-                                                  diazole-2-carbonitrile                                                                           0.1         99.5                                           5-methylsulfonyl-1,3,4-                                                       thiadiazole-2-carboxylic                                                                         0.1         90                                             acid-ethylamide                                                               5-methylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                       0.1         90                                             isopropylamide                                                                5-methylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                       0.1         90                                             propylamide                                                                   5-methylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                       0.1         90                                             butylamide                                                                    5-propylsulfonyl-1,3,4-thiadia-                                               zole-2-carboxylic acid-                                                                          0.1         93                                             allylamide                                                                    5-sec.-butylsulfonyl-1,3,4-thia-                                              diazole-2-carbonitrile                                                                           0.1         99.5                                           5-propylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                       0.1         90                                             isopropylamide                                                                5-methylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                       0.1         94                                             allylamide                                                                    5-propylsulfinyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                       0.1         90                                             ethylamide                                                                    5-propylsulfinyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                       0.1         93                                             propylamide                                                                   5-methylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                       0.1         90                                             (3-methoxypropyl)-amide                                                       5-methylsulfinyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                       0.1         90                                             ethylamide                                                                    5-methylsulfinyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                       0.1         90                                             isopropylamide                                                                5-propylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                       0.1         93                                             dimethylamide                                                                 5-butylsulfinyl-1,3,4-thia-                                                   diazole-2-carboxamide                                                                            0.1         93                                             5-isobutylsulfonyl-1,3,4-thia-                                                diazole-2-carbonitrile                                                                           0.1         100                                            5-propylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                       0.1         95                                             hexylamide                                                                    5-isopropylsulfonyl-1,3,4-thia-                                               diazole-2-carboxylic acid-                                                                       0.1         98                                             cyclohexylmethylamide                                                         Comparison compound                                                           "Blasticidin-S" (antibiotic from                                                                 0.02        90                                             Streptomyces griseochromogenes)                                                                  0.1         97                                             ______________________________________                                    

EXAMPLE 21 Seed treatment in open field tests regarding infestation byTilletia caries

1 kg of oat seeds each was contaminated with 5 g of spores of the causeof the stinking smuts disease, Tilletia caries. Part of the seeds wasthen treated with the active agents listed below in the table andanother part was untreated. All the seeds were then planted in openfields.

The active agents were employed in the form of pulverulent compositions.After about 9 months in case of winter oats and after about 4 months incase of summer oats the diseased heads were counted and on that basisthe activity was calculated by the following formula: ##EQU5##

    ______________________________________                                                        g active agent/                                                               100 kg winter oats                                                                           % activity                                     ______________________________________                                        Active agent                                                                  5-methylsulfonyl-1,3,4-                                                                       25             100                                            thiadiazole-2-carboxamide                                                                     50             100                                                            100            100                                            5-methylsulfonyl-1,3,4-thia-                                                                  25             --                                             diazole-2-carboxylic acid-                                                                    50             --                                             cyclohexyl-methylamide                                                                        100            100                                            5-isopropylsulfonyl-1,3,4-                                                                    25             --                                             thiadiazole-2-carbonitrile                                                                    50             --                                                             100            100                                            Comparison compound                                                           Methoxyethyl-Hg-silicate                                                                      5.3             99                                            Untreated 7.1% infestation                                                    ______________________________________                                                        summer oats                                                   ______________________________________                                        Active agent                                                                  5-ethylsulfinyl-1,3,4-thia-                                                                   25             100                                            diazole-2-carboxamide                                                                         50             100                                            5-methylsulfonyl-1,3,4-                                                       thiadiazole-2-carboxylic                                                                      25             --                                             acid-methylamide                                                                              50             100                                            5-isobutylsulfonyl-1,3,4-                                                                     25             --                                             thiadiazole-2-carboxamide                                                                     50              99                                            Comparison compound                                                           Methoxyethyl-Hg-silicate                                                                      2.6             99                                            Untreated 34.5% infestation                                                   ______________________________________                                    

EXAMPLE 22 Seed treatment in open field tests for infestation byHelminthosporium gramineum

Barley seeds which had a natural infestation of Helminthosporiumgramineum which causes the streak disease were seeded in open fields.Part of the seeds had been treated with the active agents listed in thetable below and another part had been left untreated.

The active agents were used in the form of pulverulent compositions.After about 8 months in case of winter barley and after about 3 monthsin case of summer barely the infested plants were counted and theactivity was calculated by the formula ##EQU6##

    ______________________________________                                                        g active agent/                                                               100 kg barley                                                                            % activity                                         ______________________________________                                        Active agent      Winter barley                                               5-methylsulfonyl-1,3,4-thia-                                                                    25           90                                             diazole-2-carboxamide                                                                           50           96                                                               75           100                                                              100          100                                            5-isopropylsulfonyl-1,3,4-                                                                      25           --                                             thiadiazole-2-carbonitrile                                                                      50           --                                                               75           99                                                               100          100                                            5-methylsulfonyl-1,3,4-thia-                                                                    25           99.5                                           diazole-2-carboxylic acid-                                                                      50           99.5                                           methylamide       75           100                                            5-methylsulfonyl-1,3,4-thia-                                                                    25           --                                             diazole-2-carboxylic acid-                                                                      50           98                                             dimethylamide     75           --                                                               100          100                                            5-isobutylsulfonyl-1,3,4-                                                                       25           --                                             thiadiazole-2-carboxamide                                                                       50           100                                                              75           100                                                              100          100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     25           --                                             diazole-2-carboxylic acid-                                                                      50           100                                            methylamide       75           --                                                               100          100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     25           --                                             diazole-2-carboxylic acid-                                                                      50           99.5                                           dimethylamide     75           --                                                               100          100                                            Comparison compound                                                           Methoxyethyl-Hg-silicate                                                                        5.2          100                                                              2.6          99.4                                           Untreated 11.2% infestation                                                   Active agent      Summer barley                                               5-methylsulfonyl-1,3,4-                                                                         25           95                                             thiadiazole-2-carboxamide                                                                       50           100                                                              100          100                                            5-isopropylsulfonyl-1,3,4-                                                                      25           100                                            thiadiazole-2-carbonitrile                                                                      50           99.8                                                             100          100                                            5-methylsulfonyl-1,3,4-                                                                         25           93                                             thiadiazole-2-carboxylic                                                                        50           100                                            acid-methylamide  100          100                                            5-isobutylsulfonyl-1,3,4-                                                                       25           --                                             thiadiazole-2-carboxamide                                                                       50           99.5                                                             100          100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     25           --                                             diazole-2-carboxylic acid-                                                                      50           100                                            methylamide       100          100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     25           --                                             diazole-2-carboxylic acid-                                                                      50           99.5                                           dimethylamide     100          100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     25           --                                             diazole-2-carboxylic acid-                                                                      50           --                                             butylamide        100          100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     25           --                                             diazole-2-carboxylic acid-                                                                      50           --                                             cyclopropylamide  200          100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     25           98                                             diazole-2-carboxylic acid-                                                                      50           99.5                                           ethylamide        100          100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     25           95                                             diazole-2-carboxylic acid-                                                                      50           99.3                                           propylamide       100          100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     25           94                                             diazole-2-carboxylic acid-                                                                      50           96.9                                           (N-butyl-N-methyl)-amide                                                                        100          99.5                                           5-ethylsulfonyl-1,3,4-thia-                                                                     25           92                                             diazole-2-carboxylic acid-                                                                      50           98                                             (2-methoxyethyl)-amide                                                                          100          99.8                                           5-ethylsulfonyl-1,3,4-thia-                                                                     25           94                                             diazole-2-carboxylic acid-                                                                      50           96                                             (3-methoxypropyl)-amide                                                                         100          100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     25           96                                             diazole-2-carboxylic acid-                                                                      50           100                                            isopropyl-amide   100          99.8                                           5-ethylsulfonyl-1,3,4-thia-                                                                     25           97                                             diazole-2-carboxylic acid-                                                                      50           100                                            allylamide        100          100                                            5-ethylsulfonyl-1,3,4-thia-                                                                     25           --                                             diazole-2-carboxylic acid-                                                                      50           100                                            N,N-tetramethyleneamide                                                                         100          --                                             5-ethylsulfonyl-1,3,4-thia-                                                                     25           --                                             diazole-2-carboxylic acid-                                                                      50           99.3                                           (N,N-3-oxapentamethyleneamide)                                                                  100          --                                             5-propylsulfinyl-1,3,4-thia-                                                                    25           --                                             diazole-2-carbonitrile                                                                          50           99.3                                                             100          --                                             5-ethylsulfinyl-1,3,4-thia-                                                                     25           --                                             diazole-2-carbonitrile                                                                          50           100                                                              100          --                                             5-methylsulfonyl-1,3,4-thia-                                                                    25           --                                             diazole-2-carboxylic acid-                                                                      50           100                                            ethylamide        100          --                                             5-methylsulfonyl-1,3,4-thia-                                                                    25           --                                             diazole-2-carboxylic acid-                                                                      50           100                                            isopropylamide    100          --                                             5-methylsulfonyl-1,3,4-thia-                                                                    25           --                                             diazole-2-carboxylic acid-                                                                      50           100                                            propylamide       100          --                                             5-methylsulfonyl-1,3,4-thia-                                                                    25           --                                             diazole-2-carboxylic acid-                                                                      50           99.3                                           butylamide        100          --                                             5-methylsulfinyl-1,3,4-thia-                                                                    25           --                                             diazole-2-carboxylic acid-                                                                      50           97                                             propylamide       100          --                                             5-methylsulfinyl-1,3,4-thia-                                                                    25           --                                             diazole-2-carboxylic acid-                                                                      50           100                                            butylamide        100          --                                             5-sec.-butylsulfonyl-1,3,4-                                                                     25           --                                             thiadiazole-2-carboxyamide                                                                      50           94                                                               100          --                                             5-methylsulfinyl-1,3,4-thia-                                                                    25           --                                             diazole-2-carboxylic acid-                                                                      50           100                                            allylamide        100          --                                             Comparison compound                                                           Methoxyethyl-Hg-silicate                                                                        10.4         100                                                              5.2          99.8                                           Untreated 23.9% infestation                                                   ______________________________________                                    

EXAMPLE 23 Oat seed treatment for Ustilago avenae

Oat seeds were dipped into a suspension of the spores of Ustilago avenaewhich causes the oat smuts fungus. The seeds were then exposed in avacuum desiccator several times to a change from atmospheric tosubatmospheric pressure. After drying the seeds were treated with theactive agents listed in the subsequent table. These agents were used inthe form of pulverulent compositions. 10 weeks after seeding thediseased pancicles were counted and on this basis the activity wascalculated by the formula ##EQU7##

    ______________________________________                                                      g active agent/                                                               100 kg       % activity                                         ______________________________________                                        Active agent                                                                  5-methylsulfonyl-1,3,4-thia-                                                                  100            84                                             diazole-2-carboxamide                                                                         150            90                                             5-isopropylsulfonyl-1,3,4-                                                                    100            97                                             thiadiazole-2-carbonitrile                                                                    150            --                                             5-methylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid-                                                                    100            90                                             methylamide     150            --                                             5-isobutylsulfonyl-1,3,4-                                                                     100            87                                             thiadiazole-2-carboxamide                                                                     150            --                                             Comparison compound                                                           Methoxyethyl-Hg-silicate                                                                       16            66                                             Untreated 16.6% infestation                                                   ______________________________________                                    

EXAMPLE 24 Effects of prophylactic leaf treatment of grapevines in thehothouse against Plasmopara viticola

Young grapevine plants having from 5 to 8 leaves were sprayed drippingwet with the concentrations of active agents stated in the table below.After drying of the spray deposit the leaves were sprayed with anaqueous suspension of sporangia of the fungus (about 20,000 per ml); thespraying was applied to the bottom side of the leaves. The plants werethen immediately incubated in a hothouse at a temperature of 22° to 24°C. and at maximum water saturation in the atmosphere. Beginning with thesecond day the humidity of the air was reduced for 3 to 4 days to normallevel (30 to 70% saturation) and was then maintained for another day onthe level of full saturation. Subsequently, the percentage portion ofthe fungus infested surface of each leaf was noted and the average pertreatment was calculated in order to determine the fungicidal activity.This was done on the basis of the following formula: ##EQU8##

The active compounds were applied in the form of a 20% concentrationspray powder.

    ______________________________________                                                         Concentration                                                Active agent     of active agent                                                                            % activity                                      ______________________________________                                        5-methylsulfonyl-1,3,4-thia-                                                                   0.001        76                                              diazole-2-carboxylic acid-                                                                     0.005        88                                              hexahydrobenzylamide                                                                           0.025        97                                              5-propylsulfonyl-1,3,4-                                                                        0.001        --                                              thiadiazole-2-carboxamide                                                                      0.005        89                                                               0.025        95                                              5-ethylsulfonyl-1,3,4-thia-                                                                    0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        --                                              ethylamide       0.025        98                                              5-ethylsulfonyl-1,3,4-thia-                                                                    0.001        100                                             diazole-2-carboxylic acid-                                                                     0.005        100                                             (N-butyl-N-methyl)-amide                                                                       0.025        100                                             5-ethylsulfonyl-1,3,4-thia-                                                                    0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        --                                              (3-methoxypropyl)-amide                                                                        0.025        90                                              5-ethylsulfonyl-1,3,4-thia-                                                                    0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        --                                              isopropyl-amide  0.025        92                                              5-ethylsulfonyl-1,3,4-thia-                                                                    0.001        98                                              diazole-2-carboxylic acid-                                                                     0.005        96                                              allylamide       0.025        99.4                                            5-ethylsulfonyl-1,3,4-thia-                                                                    0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        --                                              octylamide       0.025        90                                              5-ethylsulfonyl-1,3,4-thia-                                                                    0.001        91                                              diazole-2-carboxylic acid-                                                                     0.005        99                                              N,N-tetramethyleneamide                                                                        0.025        100                                             5-propylsulfinyl-1,3,4-                                                                        0.001        100                                             thiadiazole-2-carbonitrile                                                                     0.005        100                                                              0.025        100                                             5-ethylsulfinyl-1,3,4-                                                                         0.001        89                                              thiadiazole-2-carbonitrile                                                                     0.005        96                                                               0.025        100                                             5-methylsulfonyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        81                                              ethylamide       0.025        97                                              5-methylsulfonyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        76                                              isopropylamide   0.025        96                                              5-methylsulfonyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        82                                              propylamide      0.025        95                                              5-methylsulfonyl-1,3,4-thia                                                                    0.001        83                                              diazole-2-carboxylic acid-                                                                     0.005        99.1                                            butylamide       0.025        99.2                                            5-methylsulfinyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        75                                              propylamide      0.025        99                                              5-methylsulfinyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        --                                              butylamide       0.025        93                                              5-propylsulfonyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        --                                              propylamide      0.025        93                                              5-methylsulfinyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        --                                              allylamide       0.025        90                                              5-methylsulfinyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        --                                              (2-methoxyethyl)-amide                                                                         0.025        96                                              5-methylsulfinyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        --                                              ethylamide       0.025        96                                              5-methylsulfinyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        --                                              isopropylamide   0.025        90                                              5-methylsulfinyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        80                                              cyclopropylamide 0.025        90                                              5-methylsulfonyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        84                                              N,N-trimethyleneamide                                                                          0.025        90                                              5-methylsulfinyl-1,3,4-thia-                                                                   0.001        86                                              diazole-2-carboxylic acid-                                                                     0.005        93                                              N,N-trimethyleneamide                                                                          0.025        94                                              5-propylsulfonyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        75                                              dimethylamide    0.025        90                                              5-butylsulfonyl-1,3,4-thia-                                                                    0.001        --                                              diazole-2-carboxamide                                                                          0.005        73                                                               0.025        90                                              5-butylsulfinyl-1,3,4-thia-                                                                    0.001        75                                              diazole-2-carboxamide                                                                          0.005        99.8                                                             0.025        100                                             5-butylsulfonyl-1,3,4-thia-                                                                    0.001        --                                              diazole-2-carbonitrile                                                                         0.005        91                                                               0.025        93                                              5-isobutylsulfonyl-1,3,4-thia-                                                                 0.001        79                                              diazole-2-carbonitrile                                                                         0.005        87                                                               0.025        99                                              5-propylsulfonyl-1,3,4-thia-                                                                   0.001        88                                              diazole-2-carboxylic acid-                                                                     0.005        98                                              hexylamide       0.025        100                                             5-isopropylsulfonyl-1,3,4-thia-                                                                0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        92                                              cyclohexylmethylamide                                                                          0.025        97                                              5-propylsulfinyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carboxylic acid-                                                                     0.005        91                                              butylamide       0.025        99.1                                            5-propylsulfinyl-1,3,4-thia-                                                                   0.001        86                                              diazole-2-carboxylic acid-                                                                     0.005        92                                              sec.-butylamide  0.025        92                                              5-propylsulfinyl-1,3,4-thia-                                                                   0.001        95                                              diazole-2-carboxylic acid-                                                                     0.005        99.1                                            hexylamide       0.025        100                                             5-pentylsulfonyl-1,3,4-thia-                                                                   0.001        --                                              diazole-2-carbonitrile                                                                         0.005        --                                                               0.025        90                                              5-hexylsulfonyl-1,3,4-                                                                         0.001        --                                              thiadiazole-2-carbonitrile                                                                     0.005        --                                                               0.025        90                                              5-hexylsulfonyl-1,3,4-                                                                         0.001        --                                              thiadiazole-2-carboxamide                                                                      0.005        --                                                               0.025        90                                              ______________________________________                                    

EXAMPLE 25 Effects of a prophylactic leaf treatment of tomato plantsagainst Botrytis cinerea

Young tomato plants were sprayed dripping wet with the concentrations ofthe active agents as indicated in the subsequent table. After drying ofthe spray deposit the treated plants and also untreated control plantswere inoculated by spraying with a suspension of spores (about 1 millionper ml of fruit juice solution) of Botrytis cinerea and were incubatedin moist condition in a hothouse at about 20° C. After the collapse ofthe untreated plants (indicating 100% infestation) the degree ofinfestation of the treated plants was determined and the fungicidalactivity was calculated on the basis of the following formula ##EQU9##

The active agents were applied in the form of 20% concentration spraypowders.

    ______________________________________                                                               % activity at a con-                                                          centration of 0.025                                    Active agent           of the active agent                                    ______________________________________                                        5-methylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-methylamide                                                                        78                                                     5-propylsulfonyl-1,3,4-thiadiazole-                                           2-carboxyamide         94                                                     5-propylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-methylamide                                                                        88                                                     5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid-octylamide                                                                         87                                                     5-ethylsulfonyl-1,3,4-thiadiazole-2                                           carboxylic acid-N,N-tetramethyleneamide                                                              75                                                     5-ethylsulfonyl-1,3,4-thiadiazole-2-                                          carboxylic acid-cyclooctylamide                                                                      93                                                     5-methylsulfonyl-1,3,4-thiadiazole-2-                                         carboxylic acid-propylamide                                                                          76                                                     5-methylsulfonyl-1,3,4-thiadiazole-2-                                         carboxylic acid-butylamide                                                                           76                                                     5-propylsulfonyl-1,3,4-thiadiazole-2-                                         carboxylic acid-propylamide                                                                          80                                                     5-methylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-ethylamide                                                                           75                                                     5-methylsulfonyl-1,3,4-thiadiazole-2-                                         carboxylic acid-cyclopropylamide                                                                     75                                                     5-propylsulfonyl-1,3,4-thiadiazole-2-                                         carboxylic acid-hexylamide                                                                           78                                                     5-propylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-butylamide                                                                           80                                                     5-propylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-sec.-butylamide                                                                      80                                                     5-propylsulfinyl-1,3,4-thiadiazole-2-                                         carboxylic acid-hexylamide                                                                           80                                                     5-propylsulfinyl-1,3,4-thiadiazole-                                           2-carboxylic acid-dimethylamide                                                                      80                                                     5-pentylsulfonyl-1,3,4-thiadiazole-                                           2-carbonitrile         86                                                     5-hexylsulfonyl-1,3,4-thiadiazole-                                            2-carbonitrile         86                                                     5-pentylsulfonyl-1,3,4-thiadiazole-                                           2-carboxamide          87                                                     5-hexylsulfonyl-1,3,4-thiadiazole-                                            2-carboxamide          87                                                     5-propylsulfonyl-1,3,4-thiadiazole-                                           2-carboxylic acid-N,N-trimethylene-                                           amide                  87                                                     ______________________________________                                    

EXAMPLE 26

Treatment of rye seeds against Fusarium nivale

Rye seeds with a natural infestation by Fusarium nivale were seeded inearth filled pots and left for germination at about 6° C. Part of theseeds was treated before seeding with the active agents as appears fromthe subsequent table and part was untreated. After emergence of theseedlings the plants were illuminated with artificial light for 12 hourseach day. After about 4 weeks the degree of infestation was determinedin percentages. The fungicidal activity was calculated on the basis ofthe following formula: ##EQU10##

The active agents were used in the form of 20% concentrationcompositions.

    ______________________________________                                                         % activity; amount                                                            of active agent:                                             Active agent     100 g/100 kg                                                 ______________________________________                                        5-methylsulfonyl-1,3,4-                                                       thiadiazole-2-carboxamide                                                                      99                                                           5-ethylsulfonyl-1,3,4-                                                        thiadiazole-2-carboxamide                                                                      99.2                                                         5-ethylsulfonyl-1,3,4-                                                        thiadiazole-2-carbonitrile                                                                     92                                                           5-ethylsulfinyl-1,3,4-                                                        thiadiazole-2-carboxamide                                                                      93                                                           5-methylsulfonyl-1,3,4-                                                       thiadiazole-2-carboxylic                                                      acid-methylamide 100                                                          5-isobutylsulfonyl-1,3,4-                                                     thiadiazole-2-carboxamide                                                                      99.2                                                         5-ethylsulfonyl-1,3,4-                                                        thiadiazole-2-carboxylic                                                      acid-methylamide 100                                                          5-ethylsulfonyl-1,3,4-thia-                                                   diazole-2-carboxylic acid-                                                    dimethylamide    100                                                          5-ethylsulfonyl-1,3,4-thia-                                                   diazole-2-carboxylic acid-                                                    allylamide       94                                                           ______________________________________                                    

EXAMPLE 27 Effects of the treatment of oat seeds against Septorianodorum

Oat seeds with a natural infestation by Septoria nodorum were treatedwith the active agents as indicated in the table below. They were thenseeded on a moist substrate for germination. As a control untreatedseeds were likewise seeded. At about 6° C. the seed was incubated in anairconditioned chamber until after 4 weeks the proportion of diseasedseeds could be determined and the activity of the fungicidal compoundswas calculated on the basis of the following formula: ##EQU11##

The active agents were applied in the form of 20% concentrationpulverulent compositions.

    ______________________________________                                                               % activity in case of                                                         50 g active agent/                                     Active agent           100 kg seeds                                           ______________________________________                                        5-methylsulfonyl-1,3,4-                                                       thiadiazole-2-carboxamide                                                                            91                                                     5-methylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid                                                     methylamide            93                                                     5-ethylsulfonyl-1,3,4-thia-                                                   diazole-2-carboxylic acid                                                     methylamide            72                                                     5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid dimethylamide                                                                      86                                                     5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid propylamide                                                                        81                                                     5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid (2-methoxyethyl)-amide                                                             86                                                     5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid (3-methoxypropyl)-                                          amide                  86                                                     5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid isopropylamide                                                                     86                                                     5-ethylsulfonyl-1,3,4-thiadiazole-                                            2-carboxylic acid allylamide                                                                         72                                                                            1.3 g active                                           Comparison compound    agent/100 kg seeds                                     ______________________________________                                        Methoxyethyl-Hg-silicate                                                                             86                                                     Untreated   75% infested                                                      ______________________________________                                    

EXAMPLE 28 Prophylactic leaf treatment of apples in open field testagainst Venturia inaequalis

Apple shoots with young leaves were treated with the agents stated inthe subsequent table until they were dripping wet. After drying of thespray deposits these shoots and also untreated shoots were inoculated byuniform spraying with a suspension of conidia spores of Venturiainaequalis in a 3% aqueous glucose solution (400,000 spores/ml).

Subsequently, each applie shoot was covered with a polyethylene bag soas to obtain favorable conditions for the infection. After more than 48hours the bags were removed. The scab infestation of the leaves wasdetermined after 3 weeks by estimating the degree of scab coverage inpercentage of each leaf surface. The activity of the fungicidal agentwas calculated on this basis by the following formula: ##EQU12##

The active agents were employed as a 50% concentration spray powder.

    ______________________________________                                                          Concentration                                                                 of active agent                                             Active agent      in grams     % activity                                     ______________________________________                                        5-isopropylsulfonyl-1,3,4-                                                    thiadiazole-2-carbonitrile                                                                      0.005        97                                                               0.025        100                                            5-methylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid                                                                       0.005        90                                             methylamide       0.025        92                                             5-isobutylsulfonyl-1,3,4-thia-                                                                  0.005        87                                             diazole-2-carboxamide                                                                           0.025        95                                             5-methylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid                                                                       0.005        81                                             ethylamide        0.025        97                                             5-methylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid                                                                       0.005        85                                             isopropylamide    0.025        100                                            5-methylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid                                                                       0.005        98                                             propylamide       0.025        99.7                                           5-methylsulfonyl-1,3,4-thia-                                                  diazole-2-carboxylic acid                                                                       0.005        94                                             butylamide        0.025        99                                             5-methylsulfinyl-1,3,4-thia-                                                  diazole-2-carboxylic acid                                                                       0.005        62                                             propylamide       0.025        99.7                                           5-methylsulfinyl-1,3,4-thia-                                                  diazole-2-carboxylic acid                                                                       0.005        86                                             butylamide        0.025        99                                             5-methylsulfinyl-1,3,4-thia-                                                  diazole-2-carboxylic acid                                                                       0.005        71                                             isopropylamide    0.025        90                                             Comparison compound                                                           2,3-dinitrilo-1,4-anthraquinone                                                                 0.005        86                                                               0.025        94                                             Untreated 96% infestation                                                     ______________________________________                                    

EXAMPLE 29 Treatment of wheat and barley seeds in open field testsagainst Ustilago nuda

Winter wheat seeds which had been infested with the smut cause Ustilagonuda tritici and winter barley seeds infested with Ustilago nuda nudawere treated with the agents listed in the table below and were seededat seeding time in open fields. As a control untreated seeds werelikewise included in the seed. After eight months the affected headswere counted for each test group and their proportion was calculated inorder to find the fungicidal activity by the following formula:##EQU13##

The active compounds were employed in the form of 20% concentrationpowder compositions.

    ______________________________________                                                    amount of                                                                     active agent                                                                             % activity                                                           in gram/100 kg                                                                             winter   winter                                    Active agent  seeds        oats     barley                                    ______________________________________                                        5-isopropylsulfonyl-                                                          1,3,4-thiadiazole-2-                                                          carbonitrile  100          70       93                                        5-isobutylsulfonyl-                                                           1,3,4-thiadiazole-2-                                                          carboxamide   100          75       79                                        Untreated                  4.33%    1.34%                                     ______________________________________                                    

Without further analysis, the foregoing will so fully reveal the gist ofthe present invention that others can, by applying current knowledge,readily adapt it for various applications without omitting featuresthat, from the standpoint of prior art, fairly constitute essentialcharacteristics of the generic or specific aspects of this invention.

What is claimed as new and desired to be protected by Letters Patent isset forth in the appended claims:
 1. A composition having fungicidal andnematocidal activity comprising as activeagent1,3,4-thiadiazole-2-carboxylic acid derivatives of the formula##STR7## wherein R is C₁ -C₆ -alkyl, C₂ -C₆ -Alkenyl, C₂ -C₆ -Alkinyl orC₃ -C₆ -Cycloalkyl, R₁ is C₁ -C₆ -alkoxycarbonyl, aminocarbonyl, C₁ -C₈-alkylaminocarbonyl, C₃ -C₆ -cycloalkylaminocarbonyl, di-C₁ -C₈alkylaminocarbonyl, cyclohexylmethylaminocarbonyl, methoxy-C₂ -C₃-alkylaminocarbonyl, morpholinocarbonyl, pyrrolidinocarbonyl,piperidinocarbonyl or cyano, and n is 0, 1 or 2,in an amount of about 1to 95% by weight and a liquid or solid carrier material in an amount ofabout 99 to 5% by weight which carrier material may be replaced in anamount up to 20% by weight by a surface active agent.